Catalysts for olefin polymerization

ABSTRACT

Transition metal complexes of selected monoanionic phosphine ligands, which also contain a selected Group 15 or 16 (IUPAC) element and which are coordinated to a Group 3 to 11 (IUPAC) transition metal or a lanthanide metal, are polymerization catalysts for the (co)polymerization of olefins such as ethylene and α-olefins, and the copolymerization of such olefins with polar group-containing olefins. These and other nickel complexes of neutral and monoanionic bidentate ligands copolymerize ethylene and polar comonomers, especially acrylates, at relatively high ethylene pressures and surprisingly high temperatures, and give good incorporation of the polar comonomers and good polymer productivity. These copolymers are often unique structures, which are described.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority under 35 U.S.C. §119 from U.S.Provisional Application Ser. Nos. 60/208,087 (filed May 31, 2000),60/211,601 (filed Jun. 15, 2000), 60/214,036 (filed Jun. 23, 2000) and60/264,537 (filed Jan. 25, 2001), all of which are incorporated byreference herein as if fully set forth.

FIELD OF THE INVENTION

[0002] Transition metal complexes of selected monoanionic phosphineligands, which also contain a selected Group 15 or 16 (IUPAC) elementand which are coordinated to a Group 3 to 11 (IUPAC) transition metal ora lanthanide metal, are polymerization catalysts for the(co)polymerization of olefins such as ethylene and α-olefins, and thecopolymerization of such olefins with polar group-containing olefins. Ingeneral, nickel complexes of neutral and monoanionic bidentate ligandscopolymerize ethylene and polar comonomers at relatively high ethylenepressures and surprisingly high temperatures.

TECHNICAL BACKGROUND

[0003] Polyolefins are very important items of commerce, largequantities of various grades of these polymers being produced annuallyfor a large number of uses, such as packaging films, elastomers andmoldings. There are many different methods for making such polymers,including many used commercially, such as free radical polymerization,and many so-called coordination catalysts such as Ziegler-Natta-type andmetallocene-type catalysts. Each of these catalyst systems has itsadvantages and disadvantages, including cost of the polymerization andthe particular monomers (co)polymerized, and structure of the polyolefinproduced. Due to the importance of polyolefins, new catalyst systemswhich are economical and/or produce new types of polyolefins areconstantly being sought.

[0004] U. Klabunde, et al., J. Mol. Cat., vol. 41, p. 123-134 (1987)describes the polymerization of ethylene with nickel complex catalystshaving certain phosphorous-oxygen ligands. The catalysts and processesof this reference are different than those of the present invention.

[0005] U. Muller, et al., Angew. Chem. Int. Ed. Eng., vol. 28, p.1011-1013 report on the interaction of Ni(COD)₂ (COD is cyclooctadiene),ethylene and a phosphorous-oxygen compound which may be a ligand. Thereis no evidence for polymerization.

[0006] K. A. Ostoja Starzewski, et al., Angew. Chem., Intl. Ed. Engl.,vol. 26, p. 63 (1987) report on the polymerization of ethylene usingcertain phosphorous-oxygen ylides and Ni(COD)₂. Ylides are not usedherein.

[0007] W. Keim, Angew. Chem. Int. Ed. Engl., vol. 22, p. 503 (1983)reports the use of nickel complexes of certain arsenic-oxygen compoundsto oligomerize ethylene. Higher molecular weight polymers are notreported.

[0008] P. Braunstein, et al., J. Chem. Soc., Dalton Trans., 1996, p.3571-3574 report that nickel complexes of certain phosphorous-nitrogencompounds oligomerize ethylene to low molecular weight olefins. Highermolecular weight polymers are not reported.

[0009] U.S. Pat. Nos. 5,714,556, 6,060,569, 6,174,975 and S. D. Ittel,et al., Chem. Rev., vol. 100, p. 1169-1203 (2000) (and referencestherein), report the use of transition metal complexes of variousphosphorous-containing ligands as catalysts for olefin polymerizations.The catalysts and processes of these references are different than thoseof the present invention.

[0010] One of the advantages of some late transition metal catalysts isthat they can incorporate polar comonomers, for example olefinic esters,in copolymerizations with hydrocarbon olefins, especially ethylene.Palladium complexes are particularly noted for this ability, whilenickel complexes often do not copolymerize polar comonomers or do soonly very poorly, see for example U.S. Pat. No. 5,866,663.

[0011] It has also been discovered that using relatively hightemperatures and high hydrocarbon olefin (ethylene) pressures oftenimproves the incorporation of the polar comonomer in the polymer formedas well as increasing the productivity of the polymerization catalyst.This is surprising in view of the observations in the literature thatincreasing temperatures usually decrease the productivity of many nickelpolymerization catalysts, see for instance U.S. Pat. No. 6,127,497 andWO00/50470.

[0012] JP-A-11292918 reports the copolymerization of methyl acrylate andethylene using certain nickel complexes as polymerization catalysts.These polymerization are carried out at low temperatures and pressures,and mostly the incorporation of methyl acrylate is reported to be verylow, and the polymers have low branching levels.

[0013] A. Michalak, et al., Organometallics, vol. 20, p. 1521-1532(2001) conclude that, using computational methods, nickel complexeshaving neutral bidentate ligands such as α-dimines should notcopolymerize ethylene and polar comonomers such as methyl acrylate.

[0014] Other references of interest concerning transition metalcomplexes and/or their use as polymerization catalysts are Keim,Organometallics, vol. 2, p. 594 (1983); I. Hirose, et al., J. Mol. Cat.,vol. 73, p. 271 (1992); and R. Soula, et al., Macromolecules, vol. 34,p. 2438-2442. None of the complexes or processes with them are claimedherein.

[0015] Other references of interest concerning polar copolymers includeU.S. Pat. Nos. 3,481,908, 3,278,495 and M. M. Marques, et al., Poly.Int., 50, 579-587 (2001).

[0016] All of the above publications are incorporated by referenceherein for all purposes as if fully set forth.

SUMMARY OF THE INVENTION

[0017] This invention concerns a “first” process for the polymerizationof olefins, comprising the step of contacting, at a temperature of about−100° C. to about +200° C., at least one polymerizable olefin with anactive polymerization catalyst comprising a Group 3 through 11 (IUPAC)transition metal or a lanthanide metal complex of a ligand of theformula (I), (II) or (XII)

[0018] wherein:

[0019] R¹ and R² are each independently hydrocarbyl, substitutedhydrocarbyl or a functional group;

[0020] Y is CR¹¹R¹², S(T), S(T)₂, P(T)Q, NR³⁶ or NR³⁶NR³⁶;

[0021] X is O, CR⁵R⁶ or NR⁵;

[0022] A is O, S, Se, N, P or As;

[0023] Z is O, Se, N, P or As;

[0024] each Q is independently hydrocarbyl or substituted hydrocarbyl;

[0025] R³, R⁴, R⁵, R⁶, R¹¹and R¹² are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group;

[0026] R⁷ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that when Z is O or Se, R⁷ is not present;

[0027] R⁸ and R⁹ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or a functional group;

[0028] R¹⁰ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group;

[0029] each T is independently ═O or ═NR³⁰;

[0030] R³⁰ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group;

[0031] R³¹ and R³² are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl or a functional group;

[0032] R³³ and R³⁴ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that each is independently an aryl substituted inat least one position vicinal to the free bond of the aryl group, oreach independently has an E_(s) of −1.0 or less;

[0033] R³⁵ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that when A is O, S or Se, R³⁵ is notpresent;

[0034] each R³⁶ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group;

[0035] m is 0 or 1;

[0036] s is 0 or 1;

[0037] n is 0 or 1; and

[0038] q is 0 or 1;

[0039] and provided that:

[0040] any two of R³, R⁴, R⁵, R⁶, R⁸ , R⁹, R¹¹ and R¹² bonded to thesame carbon atom taken together may form a functional group;

[0041] any two of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹² R³¹, R³²,R³³, R³⁴, R³⁵ and R³⁶ bonded to the same atom or vicinal to one anothertaken together may form a ring; and

[0042] when said ligand is (I), Y is C(O), Z is O, and R¹ and R² areeach independently hydrocarbyl, then R¹ and R² are each independently anaryl substituted in one position vicinal to the free bond of the arylgroup, or R¹ and R² each independently have an E_(s) of −1.0 or less.

[0043] Also described herein is a “second” process for thepolymerization of olefins, comprising the step of contacting, at atemperature of about −100° C. to about +200° C., at least onepolymerizable olefin with a compound of the formula (IV), (V) or (XIII)

[0044] wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R³⁰,R³¹, R³², R³⁵, R³⁶, Y, X, A, Z, Q, T, m, s, n and q are as definedabove;

[0045] M is a Group 3 through Group 11 transition metal or a lanthanidemetal; and

[0046] L¹ is a monodentate monoanionic ligand into which an ethylenemolecule may insert between L¹ and M, and L² is a monodentate neutralligand which may be displaced by ethylene or an empty coordination site,or L¹ and L² taken together are a monoanionic bidentate ligand intowhich ethylene may insert between said monoanionic bidentate ligand andsaid nickel atom, and each L³ is independently a monoanionic ligand andz is the oxidation state of M minus 2; and provided that;

[0047] any two of R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹¹ and R¹² bonded to the samecarbon atom taken together may form a functional group;

[0048] any two of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R³¹,R³², R³³, R³⁴, R^(35 and R) ³⁶ bonded to the same atom or vicinal to oneanother taken together may form a ring; and

[0049] when said compound is (IV), Y is C(O), Z is O, and R¹ and R² areeach independently hydrocarbyl, then R¹ and R² are each independently anaryl substituted in one position vicinal to the free bond of the arylgroup, or R¹ and R² each independently have an E_(s) of −1.0 or less.

[0050] In the above-mentioned processes, (IV), (V) and (XIII) and/or thetransition metal complexes of (I), (II) or (XII) may in and ofthemselves be active catalysts, or may be “activated” by contact with acocatalyst/activator as further described below.

[0051] The present invention also concerns the ligands of the formulas(I), (II) and (XII) above, transition metal complexes thereof, andpolymerization catalyst components comprising these transition metalcomplexes.

[0052] Also disclosed herein is a “third” process for forming anethylene/polar monomer copolymer, comprising the step of contacting,under polymerizing conditions, a nickel complex of a bidentate neutralligand or a bidentate monoanionic ligand, with a monomer componentcomprising one or more hydrocarbon olefins and one or more polarcomonomers (and other optional components such as, for example, one ormore cocatalysts and/or other additives), at a temperature of about 60°C. to about 170° C., provided that when CO is present, at least oneother polar monomer is present.

[0053] This third process also relates to an improved process forforming an ethylene/polar monomer copolymer, said process comprising thestep of contacting, under polymerizing conditions, a transition metalcomplex of a bidentate neutral ligand or a bidentate monoanionic ligand,with a monomer component comprising one or more hydrocarbon olefins andone or more polar comonomers (and other optional components such as, forexample, one or more cocatalysts and/or other additives), wherein theimprovement comprises that the transition metal is nickel, and that themonomer component and complex are contacted at a temperature of about60° C. to about 170° C., provided that when CO is present, at least oneother polar monomer is present.

[0054] This invention further concerns a “first” polymer, consistingessentially of repeat units derived from ethylene, and one or more polarolef ins of the formula H₂C═CHC(O)R³², wherein R³² is —OR³⁴ or any groupreadily derivable from it, and R³⁴ is hydrocarbyl or substitutedhydrocarbyl, wherein:

[0055] said polymer contains “first branches” of the formula—(CH₂)_(n)CH₃ and “second branches” of the formula —(CH₂)_(m)C(O)R³²,wherein m and n are independently zero or an integer of 1 or more; and

[0056] said polymer has the following structural characteristics:

[0057] (a) one or both of:

[0058] (1) the ratio of first branches wherein n is 0 to first brancheswherein n is 1 is about 3.0 or more; and

[0059] (2) the ratio of first branches wherein n is 0 to first brancheswherein n is 3 is 1.0 or more; and

[0060] (b) one or both of:

[0061] (1) the total number of first branches in which n is 0, 1, 2 and3 in said polymer is about 10 or more per 1000 CH₂ groups; and

[0062] (2) the incorporation of repeat units derived from H₂C═CHC(0)R³²is 0.3 mole percent or more based on the total repeat units derived fromthe hydrocarbonolefin and H₂C═CHC(O)R³².

[0063] This invention also concerns a “second” polymer, consistingessentially of repeat units derived from:

[0064] one or more hydrocarbon olefins, such as ethylene, and

[0065] one or more polar olefins of the formula H₂C═CHC(O)R³², whereinR³² is —OR³⁴, or any group readily derivable from it, and R³⁴ ishydrocarbyl or substituted hydrocarbyl;

[0066] wherein in said polymer incorporation of repeat units derivedfrom H₂C═CHC(O)R³² is 0.3 mole percent or more based on the total repeatunits; and

[0067] wherein said polymer has one or both of the following structuralcharacteristics:

[0068] at least 5 mole percent of said repeat units derived fromH₂C═CHC(O)R³² are present in said polymer as end groups; and

[0069] said end groups are at least 0.001 mole percent of the totalrepeat units in said polymer;

[0070] and provided that said end groups have the formula

˜˜˜˜˜˜˜—HC═CH—C(O)—R³²

[0071] wherein ˜˜˜˜˜˜˜ is the remainder of the polymer chain of said endgroup.

[0072] This invention still further concerns a “third” polymer,consisting essentially of:

[0073] repeat units derived from ethylene;

[0074] repeat units derived from one or more monomers of the formulaH₂C═CHC(O)R³², wherein each R³² is independently —OR³⁴ or any groupreadily derivable from it, and each R³⁴ is independently hydrocarbyl orsubstituted hydrocarbyl, and

[0075] repeat units derived from one or more alpha-olefins of formulasH₂C═CH— (CH₂)_(t)—H and/or H₂C═CH—R⁷⁵—G, wherein t is an integer of 1 to20, R⁷⁵ is alkylene or substituted alkylene, and G is an inertfunctional group.

[0076] These and other features and advantages of the present inventionwill be more readily understood by those of ordinary skill in the artfrom a reading of the following detailed description. It is to beappreciated that certain features of the invention which are, forclarity, described below in the context of separate embodiments, mayalso be provided in combination in a single embodiment. Conversely,various features of the invention which are, for brevity, described inthe context of a single embodiment, may also be provided separately orin any subcombination.

BRIEF DESCRIPTION OF THE DRAWINGS

[0077]FIG. 1 shows the ¹³C NMR of a copolymer of ethylene and2-phenoxyethyl acrylate (EGPEA) which also contains some homopolymer ofEGPEA, and which shows assignments of various NMR peaks.

[0078]FIG. 2 shows the ¹³C NMR of a copolymer of ethylene and hexylacrylate (HA) which also contains some homopolymer of HA, and whichshows assignments of various NMR peaks.

[0079]FIG. 3 shows the ¹³C NMR of a copolymer of ethylene and methylacrylate (MA) which also contains some homopolymer of MA, and whichshows assignments of various NMR peaks. Also shown are formulas forcalculations of the amount of homopolymer present and the amount of MAincorporated in the copolymer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0080] Herein, certain terms are used. Some of them are:

[0081] A “hydrocarbyl group” is a univalent group containing only carbonand hydrogen. As examples of hydrocarbyls may be mentioned unsubstitutedalkyls, cycloalkyls and aryls. If not otherwise stated, it is preferredthat hydrocarbyl groups (and alkyl groups) herein contain 1 to about 30carbon atoms.

[0082] By “substituted hydrocarbyl” herein is meant a hydrocarbyl groupthat contains one or more substituent groups which are inert under theprocess conditions to which the compound containing these groups issubjected (e.g., an inert functional group, see below). The substituentgroups also do not substantially detrimentally interfere with thepolymerization process or operation of the polymerization catalystsystem. If not otherwise stated, it is preferred that substitutedhydrocarbyl groups herein contain 1 to about 30 carbon atoms. Includedin the meaning of “substituted” are chains or rings containing one ormore heteroatoms, such as nitrogen, oxygen and/or sulfur, and the freevalence of the substituted hydrocarbyl may be to the heteroatom. In asubstituted hydrocarbyl, all of the hydrogens may be substituted, as intrifluoromethyl.

[0083] By “(inert) functional group” herein is meant a group other thanhydrocarbyl or substituted hydrocarbyl that is inert under the processconditions to which the compound containing the group is subjected. Thefunctional groups also do not substantially interfere with any processdescribed herein that the compound in which they are present may takepart in. Examples of functional groups include halo (fluoro, chloro,bromo and iodo), and ether such as —OR²² wherein R²² is hydrocarbyl orsubstituted hydrocarbyl. In cases in which the functional group may benear a transition metal atom the functional group should not coordinateto the metal atom more strongly than the groups in those compounds areshown as coordinating to the metal atom, that is they should notdisplace the desired coordinating group.

[0084] By a “cocatalyst” or a “catalyst activator” is meant a compoundthat reacts with a transition metal compound to form an activatedcatalyst species. One such catalyst activator is an “alkyl aluminumcompound” which, herein, is meant a compound in which at least one alkylgroup is bound to an aluminum atom. Other groups such as, for example,alkoxide, hydride and halogen may also be bound to aluminum atoms in thecompound.

[0085] By “neutral Lewis base” is meant a compound, which is not an ion,that can act as a Lewis base. Examples of such compounds include ethers,amines, sulfides and organic nitriles.

[0086] By “neutral Lewis acid” is meant a compound, which is not an ion,that can act as a Lewis acid. Examples of such compounds includeboranes, alkylaluminum compounds, aluminum halides and antimony [V]halides.

[0087] By “cationic Lewis acid” is meant a cation that can act as aLewis acid. Examples of such cations are lithium, sodium and silvercations.

[0088] By an “empty coordination site” is meant a potential coordinationsite on a transition metal atom that does not have a ligand bound to it.Thus if an olefin molecule (such as an ethylene molecule) is in theproximity of the empty coordination site, the olefin molecule maycoordinate to the metal atom.

[0089] By a “ligand into which an olefin molecule may insert between theligand and a metal atom”, or a “ligand that may add to an olefin”, ismeant a ligand coordinated to a metal atom which forms a bond (L—M) intowhich an olefin molecule (or a coordinated olefin molecule) may insertto start or continue a polymerization. For instance, with ethylene thismay take the form of the reaction (wherein L is a ligand):

[0090] By a “ligand which may be displaced by an olefin” is meant aligand coordinated to a transition metal which, when exposed to theolefin (such as ethylene), is displaced as the ligand by the olefin.

[0091] By a “monoanionic ligand” is meant a ligand with one negativecharge.

[0092] By a “neutral ligand” is meant a ligand that is not charged.

[0093] By “aryl” is meant a monovalent aromatic group in which the freevalence is to the carbon atom of an aromatic ring. An aryl may have oneor more aromatic rings which may be fused, connected by single bonds orother groups.

[0094] By “substituted aryl” is meant a monovalent aromatic groupsubstituted as set forth in the above definition of “substitutedhydrocarbyl”. Similar to an aryl, a substituted aryl may have one ormore aromatic rings which may be fused, connected by single bonds orother groups; however, when the substituted aryl has a heteroaromaticring, the free valence in the substituted aryl group can be to aheteroatom (such as nitrogen) of the heteroaromatic ring instead of acarbon.

[0095] By “aryl substituted in at least one position vicinal to the freebond of the aryl group,” is meant the bond to one of the carbon atomsnext to the free valence of the aryl group is something other thanhydrogen. For example for a phenyl group, it would mean the 2 positionof the phenyl group would have something other than hydrogen attached toit. A 1-naphthyl group already has something other than hydrogenattached to one of the vicinal carbon atoms at the fused ring junction,while a 2-napthyl group would have to be substituted in either the 1 or3 positions to meet this limitation. A preferred aryl substituted in atleast one position vicinal to the free bond of the aryl group is aphenyl group substituted in the 2 and 6 positions, and optionally in theother positions.

[0096] “Alkyl group” and “substituted alkyl group” have their usualmeaning (see above for substituted under substituted hydrocarbyl).Unless otherwise stated, alkyl groups and substituted alkyl groupspreferably have 1 to about 30 carbon atoms.

[0097] By a “styrene” herein is meant a compound of the formula

[0098] wherein R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group,all of which are inert in the polymerization process. It is preferredthat all of R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ and R⁴⁷ are hydrogen. Styrene (itself) isa preferred styrene.

[0099] By a “norbornene” is meant a compound of the formula

[0100] wherein R⁴⁰ is hydrogen or hydrocarbyl containing 1 to 20 carbonatoms. It is preferred that R⁴⁰ is hydrogen or alkyl, more preferablyhydrogen or n-alkyl, and especially preferably hydrogen. The norbornenemay be substituted by one or more hydrocarbyl, substituted hydrocarbylor functional groups in the R⁴⁰ or other positions, with the exceptionof the vinylic hydrogens, which remain. Norbornene (itself), dimethylendo-norbornene-2,3-dicarboxylate and t-butyl 5-norbornene-2-carboxylateare preferred norbornenes, with norbornene (itself) being especiallypreferred.

[0101] By a “π-allyl group” is meant a monoanionic ligand comprised of 1sp³ and two Sp² carbon atoms bound to a metal center in a delocalized η³fashion indicated by

[0102] The three carbon atoms may be substituted with other hydrocarbylgroups or functional groups.

[0103] “Vinyl group” has its usual meaning.

[0104] By a “hydrocarbon olefin” is meant an olefin containing onlycarbon and hydrogen.

[0105] By a “polar (co)monomer” or “polar olefin” is meant an olefinwhich contains elements other than carbon and hydrogen. In a “vinylpolar comonomer,” the polar group is attached directly to a vinyliccarbon atom, as in acrylic monomers. When copolymerized into a polymerthe polymer is termed a “polar copolymer”. Useful polar comonomers arefound in U.S. Pat. No. 5,866,663, WO9905189, WO9909078 and WO9837110,and S. D. Ittel, et al., Chem. Rev., vol. 100, p. 1169-1203(2000), allof which are incorporated by reference herein for all purposes as iffully set forth. Also included as a polar comonomer is CO (carbonmonoxide).

[0106] By a “bidentate” ligand is meant a ligand which occupies twocoordination sites of the same transition metal atom in a complex.

[0107] By “under polymerization conditions” is meant the conditions fora polymerization that are usually used for the particular polymerizationcatalyst system being used. These conditions include things such aspressure, temperature, catalyst and cocatalyst (if present)concentrations, the type of process such as batch, semibatch,continuous, gas phase, solution or liquid slurry etc., except asmodified by conditions specified or suggested herein. Conditionsnormally done or used with the particular polymerization catalystsystem, such as the use of hydrogen for polymer molecular weightcontrol, are also considered “under polymerization conditions”. Otherpolymerization conditions such as presence of hydrogen for molecularweight control, other polymerization catalysts, etc., are applicablewith this polymerization process and may be found in the referencescited herein.

[0108] By “E_(s)” is meant a parameter to quantify steric effects ofvarious groupings, see R. W. Taft, Jr., J. Am. Chem. Soc., vol. 74, p.3120-3128 (1952), and M. S. Newman, Steric Effects in Organic Chemistry,John Wiley & Sons, New York, 1956, p. 598-603, which are both herebyincluded by reference. For the purposes herein, the Es values are thosedescribed for o-substituted benzoates in these publications. If thevalue of E_(s) for a particular group is not known, it can be determinedby methods described in these references.

[0109] The transition metals preferred herein in the first and secondprocesses are in Groups 3 through 11 of the periodic table (IUPAC) andthe lanthanides, especially those in the 4^(th), 5^(th), 6^(th) and10^(th) periods. Suitable transition metals include Ni, Pd, Cu, Pt, Fe,Co, Ti, Zr, V, Hf, Cr, Ru, Rh and Re, with Ni, Ti, Zr, Cu and Pd beingmore preferred, and Ni, Ti and Zr being especially preferred. Preferredoxidation states for some of the transition metals are Ni[II], Ti[IV],Zr[IV], and Pd[II].

[0110] For ligand (I), Table 1 gives preferred structures. For ligand(II), Table 2 gives preferred structures. In both tables, H is hydrogen,HC is hydrocarbyl, SHC is substituted hydrocarbyl and FG is functionalgroup. TABLE 1 m n X Z R³ R⁴ R⁵ R⁶ R⁷ R¹¹ R¹² Zero Zero N HC, SHC HC,SHCH,HC, SHC Zero Zero O HC, SHC HC, SHC, FG Zero 1 O H H HC, SHC, HC, SHC,FG FG Zero 1 N H H HC, SHC H, HC, H, HC, SHC, FG SHC, FG Zero 1 S H HHC, SHC, HC, SHC, FG FG 1 Zero O O H, HC, H, HC, H, HC, H, HO, SHC SHCSHC SHC 1 1 CR⁵R⁶ O H, HC, H, HC, H H H, HC, H, HC, SHC SHC SHC SHC 1 1CR⁵R⁶ N H, HC, H, HC, H H HC, SHC H, HC, H, HC, SHC SHC SHC SHC

[0111] TABLE 2 q R⁸ R⁹ R¹⁰ Zero HC, SHC 1 H, HC H, HC HC, SHC

[0112] In all preferred (I) and (II) (and by reference correspondingstructures (IV) and (V), respectively), R¹ and R² are t-butyl, aryl orsubstituted aryl, more preferably t-butyl, and 2,6-disubstituted phenyl,especially 2,6-dimethoxyphenyl. It is believed that in most of theligands it is preferred that R¹ and R² be relatively sterically bulkygroups, for example t-butyl. Thus, for instance, 2,6-dimethylphenylwould often be favored over phenyl for R¹ and R². Thus R¹ and R² may,for example, be isopropyl, phenyl, substituted phenyl, aryl, substitutedaryl, cyclohexyl, t-butyl or 2-octyl. In another preferred form, R¹ andR² are independently aryl substituted in one position vicinal to thefree bond of the aryl group, or R¹ and R² each independently have anE_(s) of −1.0 or less, or both. By both means they may be arylsubstituted in one position vicinal to the free bond of the aryl group,and also have an E_(s) of −1.0 or less.

[0113] Any two of R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹¹ and R¹² bonded to the samecarbon atom taken together may form a functional group. By this ismeant, for instance, two of these bonds may form part of an oxo (keto)group, ═O, or an imino ═N—R, wherein R is hydrocarbyl group. Preferredtypes of functional groups (single or double bonded) include oxo,—C(O)R¹³ and —CO₂R¹³, wherein R¹³ is hydrocarbyl or substitutedhydrocarbyl.

[0114] In (I) or (IV) the following structures are preferred:

[0115] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or

[0116] the transition metal is Ti, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or

[0117] the transition metal is Zr, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹ R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or

[0118] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, R⁷ is hydrocarbyl or substituted hydrocarbyl, Y is CR¹¹R¹²,R¹¹ is hydrogen, R¹² is hydrocarbyl or substituted hydrocarbyl, and Z isN; or

[0119] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are oxo, and Z is O;or

[0120] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, R⁷ is hydrocarbyl or substituted hydrocarbyl, Y is CR¹¹R¹²,R¹¹ and R¹² taken together are oxo, and Z is N; or

[0121] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is S(T), T is ═O and Z is O; or

[0122] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is S(T), T is ═N-silyl, Z is N and R⁷ is silyl; or

[0123] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is S(T), T is ═O, Z is N, and R⁷ is hydrocarbyl orsubstituted hydrocarbyl; or

[0124] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are a ring and Z isO; or

[0125] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are N-hydrocarbyl- orN-substituted hydrocarbylimino, Z is N and R⁷ is hydrocarbyl orsubstituted hydrocarbyl; or

[0126] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is S(T), T is ═O and Z is O; or

[0127] the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are sulfo, Z is N andR⁷ is hydrocarbyl or substituted hydrocarbyl.

[0128] In (II) or (V), it is preferred that the transition metal is Ni,q is 0 or 1, R⁸ and R⁹ are hydrogen and R¹⁰ is hydrocarbyl orsubstituted hydrocarbyl.

[0129] In (XII) (and by reference corresponding structure (XIII)), R³³and R³⁴ are preferably t-butyl, aryl (other than phenyl) or substitutedaryl, more preferably t-butyl and 2,6-disubstituted phenyl, especially2,6-dimethoxyphenyl. It is believed that in most of the ligands it ispreferred that R³³ and R³⁴ be relatively sterically bulky groups, forexample t-butyl. Thus, for instance, 2,6-dimethylphenyl would often befavored over 2-methylphenyl for R³³ and R³⁴. Thus R³³ and R³⁴ may, forexample, be isopropyl, aryl (other than phenyl), substituted aryl,cyclohexyl, t-butyl or 2-octyl. In another preferred form R³³ and R³⁴are independently aryl substituted in one position vicinal to the freebond of the aryl group, or R³³ and R³⁴ each independently have an E_(s)of −1.0 or less, or both. By both means they may be aryl substituted inone position vicinal to the free bond of the aryl group, and also havean E_(s) of −1.0 or less.

[0130] As examples of useful groups R³¹ and R³² may be mentionedhydrogen, aryl, substitued aryl, oygen and nitrogen based functionalgroups and SO₃Na, as well as when R³¹ and R³² taken together form aring, for example, an aromatic or non-aromatic ring, which may includeone or more heteroatoms.

[0131] Other preferences include when A is O and s is 0.

[0132] In (IV), (V) and (XIII), useful groups L¹ include hydrocarbyl andsubstituted hydrocarbyl (especially phenyl and alkyl, and particularlyphenyl, methyl, hydride and acyl). Useful groups for L² includephosphine such as triphenylphosphine, nitrile such as acetonitrile,ethers such as ethyl ether, pyridine, and tertiary alkylamines such astriethylamine and TMEDA (N,N,N′,N′-tetramethyl-1,2-ethylenediamine).Alternatively L¹ and L² taken together may be a π-allyl or π-benzylgroup such as

[0133] wherein R is hydrocarbyl, and π-allyl and π-benzyl groups -arepreferred.

[0134] In (IV), (V) and (XIII), when an olefin (such as ethylene) mayinsert between L¹ and the transition metal atom, and L² is an emptycoordination site or is a ligand which may be displaced by an olefin(such as ethylene), or L¹ and L² taken together are a bidentatemonoanionic ligand into which an olefin (such as ethylene) may beinserted between that ligand and the transition metal atom, (IV), (V)and (XIII) may by themselves catalyze the polymerization of an olefin.

[0135] Examples of L¹ which form a bond with the metal into whichethylene may insert between it and the transition metal atom arehydrocarbyl and substituted hydrocarbyl, especially phenyl and alkyl,and particularly methyl, hydride and acyl. Ligands L² which ethylene maydisplace include phosphine such as triphenylphosphine, nitrile such asacetonitrile, ether such as ethyl ether, pyridine, tertiary alkylaminessuch as TMEDA, and other olefins. Ligands in which L¹ and L² takentogether are a bidentate monoanionic ligand into which ethylene mayinsert between that ligand and the transition metal atom includeπ-allyl- or π-benzyl-type ligands (in this instance, sometimes it may benecessary to add a neutral Lewis acid cocatalyst such as triphenylboraneor tris(pentafluoro-phenyl)borane of a cationic Lewis acid such as Li⁺to initiate the polymerization, see for instance previously incorporatedU.S. Pat. No. 6,174,975). For a summary of which ligands ethylene mayinsert into (between the ligand and transition metal atom) see forinstance J. P. Collman, et al., Principles and Applications ofOrganotransition Metal Chemistry, University Science Books, Mill Valley,Calif., 1987, included herein by reference.

[0136] If for instance the ligand in the location of L¹ is not a ligandinto which ethylene may insert between it and the transition metal atom,it may be possible to add a cocatalyst which may convert it into L¹ aligand which will undergo such an insertion. Thus if the ligand in thelocation of L¹ is halo such as chloride or bromide, a carboxylate,acetylacetonate or an alkoxide, it may be converted to hydrocarbyl suchas alkyl by use of a suitable alkylating agent such as an alkylaluminumcompound, a Grignard reagent or an alkyllithium compound. It may beconverted to hydride by use of a compound such as sodium borohydride.

[0137] As indicated above, when L¹ and L² taken together are amonoanionic bidentate ligand, a cocatalyst (sometimes also called anactivator) which is an alkylating or hydriding agent is also typicallypresent in the olefin polymerization. A preferred cocatalyst is analkylaluminum compound, and useful alkylaluminum compounds includetrialkylaluminum compounds such as triethylaluminum, trimethylaluminumand tri-i-butylaluminum, alkyl aluminum halides such as diethylaluminumchloride and ethylaluminum dichloride, and aluminoxanes such asmethylaluminoxane. More than one such cocatalyst may be used incombination.

[0138] Preferred for L³ are ligands of the type above described for L¹.

[0139] The ligands (I), (II) and (XIII) may be synthesized by a varietyof methods, depending on the particular ligand desired. The synthesis ofmany specific ligands is illustrated in the Examples. Many of thesesyntheses are accomplished through the use of R₂PLi or R₂PCH₂Li. Moregenerally speaking, the synthesis of various types of ligands isillustrated in the schemes shown below. In these schemes, each Rindependently represents hydrocarbyl or substituted hydrocarbyl, andeach R′ independently represent hydrogen, hydrocarbyl or substitutedhydrocarbyl.

[0140] In Scheme 1 one may substitute an imine for the ketone R′₂CO andobtain a final product in which Z is nitrogen rather than oxygen. Inanother variation of Scheme 1 one can react R₂PH with an acrylonitrile,followed by reaction with R′MgX (addition across the nitrile bond) andthen ((allyl)NiCl)₂ to form the 6-membered metallocycle in which Z isnitrogen. To obtain compounds in which Z is not nitrogen or oxygen, onecan use analogous compounds containing the appropriate element for Z. Asshown in Scheme 2, (II) can exist in isomeric forms, and the formula forany of the forms represents all of the isomeric forms.

[0141] Scheme 2 shows the synthesis of (II). Appropriate substitution(as in all these synthesis schemes) in these compounds may be obtainedby using appropriately substituted starting materials.

[0142] Scheme 3 shows the synthesis of 4-membered (or isomeric)metallocycles. Herein by isomeric is meant (and included in thedefinition of) that 4-membered heterocycles such as those shown inScheme 3 may also be in the form of bridged dimers and/or oligomers. Zmay be changed by using the appropriate starting material.

[0143] Scheme 4 illustrates the synthesis of a 6-membered metallocycle.The corresponding nitrogen compound may be made by using an aziridine asa starting material.

[0144] Scheme 5 illustrates a method for making (I) in which X is —O—.Herein TMEDA is tetramethylethylenediamine.

[0145] In Schemes 1-5 above Ni complexes are prepared, and for makinglate transition metal complexes other than Ni, similar reactions ofmetal compounds with an appropriate anion may be used to prepare thecomplex. Useful types of Ni compounds are listed below.

[0146] (Ph₃P)₂Ni (Ph) (Cl) which gives as ligands (in addition to (I),(II) or (XIII)) Ph and Ph₃P.

[0147] (TMEDA)₂Ni (Ph) (Cl) in the presence of a “trapping ligand” L²such as pyridine, which gives as ligands (in addition to (I), (II) or(XIII)) Ph and pyridine.

[0148] (Ph₃P)₂NiCl₂ which gives as ligands (in addition to (I), (II) or(XIII)) Cl and Ph₃P.

[0149] ((allyl)Ni(X))₂ which gives as a ligand (in addition to (I), (II)or (XII)) π-allyl.

[0150] Other useful Ni precursors and methods of synthesis of thesetypes of nickel complexes may also be found in previously incorporatedU.S. Pat. Nos. 6,060,569, 6,174,975 and S. D. Ittel, et al., Chem. Rev.,vol. 100, p. 1169-1203(2000), as well as WO98/42664, and R. H. Grubbs.,et al., Organometallics, vol. 17, p. 3149 (1988), which are alsoincorporated herein by reference for all purposes as if fully set forth.

[0151] In preparing early transition metal complexes such as Zr and Ticomplexes, the anion may be reacted with a simple metal compound such asa halide, for example ZrCl₄ or TiCl₄.

[0152] Useful monomers (olefins) include hydrocarbon olefins such asethylene and α-olefins of the formula H₂C═CH(CH₂)_(t)H (III) wherein tis an integer of 1 to 20, a styrene, a norbornene and cyclopentene; andpolar comonomers such as CO and polar olefins. Useful polar olefinsinclude those of the formula H₂C═CHR¹³E, wherein R¹³ is alkylene,alkylidene or a covalent bond, especially —(CH₂)_(x)— wherein x is 0 oran integer of 1 to 20 and E is a polar group. Useful polar groups Einclude —CO₂R¹⁴, —OC(O)R¹⁴, —CO₂H, —C(O)NR¹⁴ ₂ and —OR¹⁴, and —CO₂R¹⁴and —OR¹⁴ are more preferred, wherein each R¹⁴ is hydrogen, hydrocarbylor substituted hydrocarbyl, preferably alkyl or substituted alkyl. Forany olefin other than a norbornene, cyclopentene and a styrene, it ispreferred that it be copolymerized with ethylene. An especiallypreferred olefin is ethylene (alone). Typically CO and polar comonomerswill be used with a hydrocarbon olefin such as ethylene to form acopolymer, and often when CO is used at least one other polar monomerwill also be present.

[0153] It will be understood that not every combination of every ligandwith every transition metal will polymerize every (type of) olefin orcombination of olefins described herein. For instance, late transitionmetals are believed to be more efficacious for polymerization of polarolefins than are early transition metals. The structure of thepolyolefin produced will also vary with the particular transition metaland ligand chosen. For example late transition metals tend to producepolymers with an unusual branching pattern, while early transitionmetals give polymers with more “normal” branching patterns. For adescription of unusual and normal branching patterns see U.S. Pat. No.5,880,241, which is incorporated by reference herein for all purposes asif fully set forth. The combinations of ingredients to use in thepolymerization and the products produced may be readily determined byexperimentation.

[0154] It is preferred that the polymer produced by the first and secondprocesses herein have a degree of polymerization (average number ofmonomer units in a polymer molecule) of at least about 20, morepreferably at least about 40, and especially preferably at least about100.

[0155] In the first and second polymerization processes herein, thetemperature at which the polymerization is carried out is generallyabout −100° C. to about +200° C., preferably about −60° C. to about 150°C., and more preferably about −20° C. to about 100° C. The pressure ofthe olefin (if it is a gas) at which the polymerization is carried outis preferably atmospheric pressure to about 275 MPa.

[0156] The first and second polymerization processes herein may be runin the presence of various liquids, particularly aprotic organicliquids. The catalyst system, monomer(s), and polymer may be soluble orinsoluble in these liquids, but obviously these liquids should notprevent the polymerization from occurring. Suitable liquids includealkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatichydrocarbons. Specific useful solvents include hexane, toluene, benzene,methylene chloride, chlorobenzene, p-xylene, and 1,2,4-trichlorobenzene.

[0157] Cocatalysts such as alkylaluminum compounds and/or boranes and/orother Lewis acids may optionally be present in the first and secondprocesses. It is believed that the presence of certain Lewis acids mayenhance the productivity of the catalyst and/or the rate ofpolymerization of the olefin(s). Also Lewis acids may form so-calledZwitterionic complexes which are also useful in these processes. For anexplanation of Zwitterionic complexes, see U.S. patent application______ (filed concurrently on May 31, 2001, Applicant's reference CL1655US NA), which is hereby incorporated by reference herein for allpurposes as if fully set forth.

[0158] In the third polymerization process described herein one or morepolar comonomers are used with one or more hydrocarbon olefins, andpreferably ethylene, to form a polar copolymer. Useful polar comonomersinclude, but are not limited to compounds of the formula H₂C═CHR²⁰C(O)Y(X), H₂C═CHR^(°)CN (XI), H₂C═CR²⁵C(O)Y (XII), or H₂C═CHR²⁰CCN, whereinR²⁰ is alkylene or substituted alkylene, R²⁵ is hydrogen, and Y is —OH,—NR²¹R²², —OR²³, and —SR²⁴, wherein R²¹ and R²² are each independentlyhydrogen, hydrocarbyl or substituted hydrocarbyl, R²³ and R²⁴ are eachhydrocarbyl or substituted hydrocarbyl, and R²⁵ is hydrogen. Moregenerally vinyl polar monomers of the formula H₂C═CHX, wherein X is apolar group, are preferred. Other more specific preferred polarcomonomers are (X) wherein R²⁰ is —(CH₂)q— wherein q is 0 or an integerof 1 to 20 and Y is —OR²³, and (XII), wherein it is especially preferredthat q is zero. Norbornenes containing functional groups are also usefulpolar comonomers.

[0159] Some of Ni complexes which may contain bidentate ligands and maybe useful in the third process herein may be found in JP-A-11158214,JP-A-11158213, JP-A-10017617, JP-A-09255713, JP-A-11180991,JP-A-256414(2000), JP-A-10007718, JP-A-10182679, JP-A-128922(2000),JP-A-10324709, JP-A-344821(2000), JP-A-11292917, JP-A-11181014,WO00/56744, WO96/37522, WO96/37523, WO98/49208, WO00/18776, WO00/56785,WO/00/06620, WO99/50320, WO00/68280, WO00/59956, WO00/50475, WO00/50470,WO98/42665, WO99/54364, WO98/33823, WO99/32226, WO99/49969, WO99/15569,WO99/46271, WO98/03521, WO00/59961, DE-A-19929131, U.S. Pat. Nos.5,886,224, 5,714,556, 6,060,569, 6,069,110, 6,174,976, 6,103,658,6,200,925, 5,929,181, 5,932,670, 6,030,917, 4,689,437, EP-A-0950667 andEP-A-0942010, and S. D. Ittel, et al., Chem. Rev., vol. 100, p.1169-1203 (2000) (and references therein), all of which are herebyincorporated by reference for all purposes as if fully set forth, aswell as the complexes described herein derived from (I), (II) or (XII).

[0160] All of the complexes mentioned in these publications, and allnickel complexes of bidentate neutral and monoanionic ligands, may notin general be catalysts for the copolymerization of ethylene and one ormore polar comonomers, but the conditions described herein give a goodchance for them to be such catalysts. To determine whether such acomplex is a polar olefin copolymerization catalyst, one may simply trya copolymerization of ethylene and a polar comonomer such as methylacrylate or ethyl-10-undecylenoate under the conditions describedherein. These conditions include principally temperature and ethylenepressure. During most polymerizations there are other conditions usuallypresent, such as activation of the polymerization catalyst, exclusion ofpolymerization catalyst poisons, use of a molecular weight regulatingcompound such as hydrogen, agitation, supportation, etc. Except forthose conditions specifically described herein for the thirdpolymerization, the other conditions described, for example, in theabove references may be used in such test polymerizations and inpolymerizations of the third process in general, and reference may behad thereto for further details.

[0161] In the third process herein a preferred low temperature is about80° C., more preferably about 90° C., and a preferred high temperatureis about 150° C., more preferably about 130° C. A preferred lowerethylene pressure is about 5 MPa or more. A preferred upper limit onethylene pressure is about 200 MPa, more preferably about 20 MPa.

[0162] Preferred bidentate ligands in the third process herein are:

[0163] wherein:

[0164] R²⁶ and R²⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it;

[0165] R²⁸ and R²⁹ are each independently hydrogen, hydrocarbyl,substituted hydrocarbyl, or R²⁸ and R²⁹ taken together arehydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring;

[0166] R⁶⁰ and R⁶¹ are each independently functional groups bound to therest of (XV) through heteroatoms (for example O, S or N), or R⁶⁰ and R⁶¹(still containing their heteroatoms) taken together form a ring.

[0167] each R⁵⁰ is independently hydrocarbyl or substituted hydrocarbyl;

[0168] each R⁵¹ is independently hydrogen, hydrocarbyl or substitutedhydrocarbyl; and

[0169] each R⁵² is hydrocarbyl, substituted hydrocarbyl, hydrocarbyloxy,or substituted hydrocarbyloxy.

[0170] When (XVI), (XVII) and (XVIII) are used as the complexes,especially as their nickel complexes it is preferred that they be usedas their complexes with Lewis acids (“Zwitterionic complexes”) such astris(pentafluorophenyl)borane. These Zwitterionic complexes aresometimes better polymerization catalysts than the complexes which aredo not contain the Lewis acid. These Zwitterionic compounds may beformed before the complex is added to the polymerization process, or maybe formed in situ by reaction with Lewis acid which is present.

[0171] Other copolymerizable olefins may also be present in the thirdprocess. α-Olefins of the formula H₂C═CH(CH₂)_(z)CH₃ wherein z is 0 oran integer of 1 to 21, for example propylene or 1-butene, may be used.It is preferred that any other comonomers present constitute less than50 mole percent, more preferably less than 25 mole percent of theproduct copolymer.

[0172] One problem noted with using some polar comonomers, for exampleacrylate-type comonomers, under certain conditions is the tendency ofthese comonomers to form homopolymers. It is believed that thesehomopolymers arise from a “competitive” free radical-type polymerization“originating” from some free radicals which may be present or generatedin the third process polymerization. Some types of polar comonomers suchas acrylates are well known to readily undergo such polymerizations.These usually unwanted free radical polymerizations may be suppressed tovarying extents by the presence of free radical polymerizationinhibitors such as phenothiazine in the third polymerization process,but these may interfere with the desired polymerization process, orcause other problems. This may be particularly acute in the thirdpolymerization process herein because of the relatively high processtemperatures. It has been found that the presence of alkali metal orammonium salts, preferably alkali metal salts, of relativelynoncoordinating anions in the third polymerization process retards oreliminates the formation of homopolymer of the polar comonomer (orcopolymers containing only polar comonomers if more than one polarcomonomer is used). Particularly preferred alkali metal cations are Li,Na and K, and Li and Na are especially preferred. Useful weaklycoordinating anions include BAF, tetrakis(pentafluorophenyl)borate,N(S(O)₂CF₃)₂ ⁻, tetraphenyl-borate, trifluoromethanesulfonate, andhexafluoroantimonate, and preferred anions are BAF,tetrakis(pentafluorophenyl)-borate, and N(S(O)₂CF₃)₂ ⁻. A useful molarratio of these salts to the number of moles of Ni compounds present isabout 10,000 to about 5 to 1.0, more preferably about 1,000 to about 50to 1.0. These salts will preferably be used in a third polymerizationprocess in which there is a liquid phase present, for example apolymerization which is a solution or liquid suspension polymerization.

[0173] In any of the polymerization processes herein in which a polarcomonomer is copolymerized, and any formation of any polar copolymer, itis preferred that the molar ratio of the total of the polar comonomerspresent to any added Lewis acid is at least 2:1, preferably at least10:1. Polar comonomers, such acrylic-type monomers, have beencopolymerized in certain situations by destroying their Lewis basic (orcoordinating) character by reacting them with a Lewis acid, to form aLewis acid “salt” of the polar comonomer. While this may often help toform the polar copolymer, later removal of the stoichiometric amount (ofpolar comonomer) of Lewis acid is difficult and expensive.

[0174] The olefin polymerizations herein may also initially be carriedout in the “solid state” by, for instance, supporting the transitionmetal compound on a substrate such as silica or alumina, activating itif necessary with one or more cocatalysts and contacting it with theolefin(s). Alternatively, the support may first be contacted (reacted)with one or more cocatalysts (if needed) such as an alkylaluminumcompound, and then contacted with an appropriate Ni compound. Thesupport may also be able to take the place of a Lewis or Bronsted acid,for instance, an acidic clay such as montmorillonite, if needed. Anothermethod of making a supported catalyst is to start a polymerization or atleast make a transition metal complex of another olefin or oligomer ofan olefin such as cyclopentene on a support such as silica or alumina.These “heterogeneous” catalysts may be used to catalyze polymerizationin the gas phase or the liquid phase. By gas phase is meant that agaseous olefin is transported to contact with the catalyst particle. Forthe copolymerization of polar olefins using supported catalysts,especially in a liquid medium, a preferred case is when the ligand iscovalently attached to the supports, which helps prevent leaching of thetransition metal complex from the support.

[0175] In all of the polymerization processes described herein oligomersand polymers of the various olefins are made. They may range inmolecular weight from oligomeric olefins, to lower molecular weight oilsand waxes, to higher molecular weight polyolefins. One preferred productis a polymer with a degree of polymerization (DP) of about 10 or more,preferably about 40 or more. By “DP” is meant the average number ofrepeat (monomer) units in a polymer molecule.

[0176] Depending on their properties, the polymers made by the first andsecond processes described herein are useful in many ways. For instanceif they are thermoplastics, they may be used as molding resins, forextrusion, films, etc. If they are elastomeric, they may be used aselastomers. If they contain functionalized monomers such as acrylateesters, they are useful for other purposes, see for instance previouslyincorporated U.S. Pat. No. 5,880,241.

[0177] Depending on the process conditions used and the polymerizationcatalyst system chosen, polymers, even those made from the samemonomer(s) may have varying properties. Some of the properties that maychange are molecular weight and molecular weight distribution,crystallinity, melting point, and glass transition temperature. Exceptfor molecular weight and molecular weight distribution, branching canaffect all the other properties mentioned, and branching may be varied(using the same transition metal compound) using methods described inpreviously incorporated U.S. Pat. No. 5,880,241.

[0178] It is known that blends of distinct polymers, varying forinstance in the properties listed above, may have advantageousproperties compared to “single” polymers. For instance it is known thatpolymers with broad or bimodal molecular weight distributions may bemelt processed (be shaped) more easily than narrower molecular weightdistribution polymers. Thermoplastics such as crystalline polymers mayoften be toughened by blending with elastomeric polymers.

[0179] Therefore, methods of producing polymers which inherently producepolymer blends are useful especially if a later separate (and expensive)polymer mixing step can be avoided. However in such polymerizations oneshould be aware that two different catalysts may interfere with oneanother, or interact in such a way as to give a single polymer.

[0180] In such a process the transition metal containing polymerizationcatalyst disclosed herein can be termed the first active polymerizationcatalyst. Monomers useful with these catalysts are those described (andalso preferred) above. A second active polymerization catalyst (andoptionally one or more others) is used in conjunction with the firstactive polymerization catalyst. The second active polymerizationcatalyst may be a late transition metal catalyst, for example asdescribed herein, in previously incorporated U.S. Pat. Nos. 5,880,241,6,060,569, 6,174,975 and U.S. Pat. No. 5714556, and/or in U.S. Pat. No.5,955,555 (also incorporated by reference herein for all purposes as iffully set forth). Other useful types of catalysts may also be used forthe second active polymerization catalyst. For instance so-calledZiegler-Natta and/or metallocene-type catalysts may also be used. Thesetypes of catalysts are well known in the polyolefin field, see forinstance Angew. Chem., Int. Ed. Engl., vol. 34, p. 1143-1170 (1995),EP-A-0416815 and U.S. Pat. No. 5,198,401 for information aboutmetallocene-type catalysts; and J. Boor Jr., Ziegler-Natta Catalysts andPolymerizations, Academic Press, New York, 1979 for information aboutZiegler-Natta-type catalysts, all of which are hereby included byreference. Many of the useful polymerization conditions for all of thesetypes of catalysts and the first active polymerization catalystscoincide, so conditions for the polymerizations with first and secondactive polymerization catalysts are easily accessible. Oftentimes the“co-catalyst” or “activator” is needed for metallocene orZiegler-Natta-type polymerizations. In many instances the same compound,such as an alkylaluminum compound, may be used as an “activator” forsome or all of these various polymerization catalysts.

[0181] In one preferred process described herein the first olefin(s)(the monomer(s) polymerized by the first active polymerization catalyst)and second olefin(s) (the monomer(s) polymerized by the second activepolymerization catalyst) are identical, and preferred olefins in such aprocess are the same as described immediately above. The first and/orsecond olefins may also be a single olefin or a mixture of olefins tomake a copolymer. Again it is preferred that they be identicalparticularly in a process in which polymerization by the first andsecond active polymerization catalysts make polymer simultaneously.

[0182] In some processes herein the first active polymerization catalystmay polymerize a monomer that may not be polymerized by said secondactive polymerization catalyst, and/or vice versa. In that instance twochemically distinct polymers may be produced. In another scenario twomonomers would be present, with one polymerization catalyst producing acopolymer, and the other polymerization catalyst producing ahomopolymer, or two copolymers may be produced which vary in the molarproportion or repeat units from the various monomers. Other analogouscombinations will be evident to the artisan.

[0183] In another variation of this process one of the polymerizationcatalysts makes an oligomer of an olefin, preferably ethylene, whicholigomer has the formula R⁷⁰CH═CH₂, wherein R⁷⁰ is n-alkyl, preferablywith an even number of carbon atoms. The other polymerization catalystin the process then (co)polymerizes this olefin, either by itself orpreferably with at least one other olefin, preferably ethylene, to forma branched polyolefin. Preparation of the oligomer (which is sometimescalled an α-olefin) by a second active polymerization-type of catalystcan be found in previously incorporated U.S. Pat. No. 5,880,241, as wellas in WO99/02472 (also incorporated by reference herein).

[0184] Likewise, conditions for such polymerizations, using catalysts ofthe second active polymerization type, will also be found in theappropriate above-mentioned references.

[0185] Two chemically different active polymerization catalysts are usedin this polymerization process. The first active polymerization catalystis described in detail above. The second active polymerization catalystmay also meet the limitations of the first active polymerizationcatalyst, but must be chemically distinct. For instance, it may have adifferent transition metal present, and/or utilize a different type ofligand and/or the same type of ligand that differs in structure betweenthe first and second active polymerization catalysts. In one preferredprocess, the ligand type and the metal are the same, but the ligandsdiffer in their substituents.

[0186] Included within the definition of two active polymerizationcatalysts are systems in which a single polymerization catalyst is addedtogether with another ligand, preferably the same type of ligand, whichcan displace the original ligand coordinated to the metal of theoriginal active polymerization catalyst, to produce in situ twodifferent polymerization catalysts.

[0187] The molar ratio of the first active polymerization catalyst tothe second active polymerization catalyst used will depend on the ratioof polymer from each catalyst desired, and the relative rate ofpolymerization of each catalyst under the process conditions. Forinstance, if one wanted to prepare a “toughened” thermoplasticpolyethylene that contained 80% crystalline polyethylene and 20% rubberypolyethylene, and the rates of polymerization of the two catalysts wereequal, then one would use a 4:1 molar ratio of the catalyst that gavecrystalline polyethylene to the catalyst that gave rubbery polyethylene.More than two active polymerization catalysts may also be used if thedesired product is to contain more than two different types of polymer.

[0188] The polymers made by the first active polymerization catalyst andthe second active polymerization catalyst may be made in sequence, i.e.,a polymerization with one (either first or second) of the catalystsfollowed by a polymerization with the other catalyst, as by using twopolymerization vessels in series. However it is preferred to carry outthe polymerization using the first and second active polymerizationcatalysts in the same vessel(s), i.e., simultaneously. This is possiblebecause in most instances the first and second active polymerizationcatalysts are compatible with each other, and they produce theirdistinctive polymers in the other catalyst's presence. Any of theprocesses applicable to the individual catalysts may be used in thispolymerization process with 2 or more catalysts, i.e., gas phase, liquidphase, continuous, etc.

[0189] Catalyst components which include transition metal complexes of(I), (II) or (XII), with or without other materials such as one or morecocatalysts and/or other polymerization catalysts are also disclosedherein. For example, such a catalyst component could include thetransition metal complex supported on a support such as alumina, silica,a polymer, magnesium chloride, sodium chloride, etc., with or withoutother components being present. It may simply be a solution of thetransition metal complex, or a slurry of the transition metal complex ina liquid, with or without a support being present.

[0190] The polymers produced by this process may vary in molecularweight and/or molecular weight distribution and/or melting point and/orlevel of crystallinity, and/or glass transition temperature and/or otherfactors. For copolymers the polymers may differ in ratios of comonomersif the different polymerization catalysts polymerize the monomerspresent at different relative rates. The polymers produced are useful asmolding and extrusion resins and in films as for packaging. They mayhave advantages such as improved melt processing, toughness and improvedlow temperature properties.

[0191] Hydrogen or other chain transfer agents such as silanes (forexample trimethylsilane or triethylsilane) may be used to lower themolecular weight of polyolefin produced in the polymerization processherein. It is preferred that the amount of hydrogen present be about0.01 to about 50 mole percent of the olefin present, preferably about 1to about 20 mole percent. When liquid monomers (olefins) are present,one may need to experiment briefly to find the relative amounts ofliquid monomers and hydrogen (as a gas). If both the hydrogen andmonomer(s) are gaseous, their relative concentrations may be regulatedby their partial pressures.

[0192] Copolymers of ethylene and certain polar comonomers such asH₂C═CHC(O)R³² are described herein (first and second polymers), and theycontain first branches of the formula —(CH₂)_(n)CH₃ and second branchesof the formula —(CH₂)_(m)C(O)R³³, wherein R³² is —OR³⁴ or any groupreadily derivable from it, R³³ is R³² or any group readily derivablefrom it, R³⁴ is hydrocarbyl or substituted hydrocarbyl, and each R³⁵ ishydrogen, hydrocarbyl or substituted hydrocarbyl. By “any group readilyderivable from it” is meant any derivative of a carboxylic acid which isreadily interconverted from the carboxylic acid itself or a derivativeof a carboxylic acid. For example a carboxylic acid ester may beconverted to a carboxylic acid by hydrolysis, an amide by reaction witha primary or secondary amine, a carboxylate salt (for example with analkali or alkaline earth metal) by hydrolysis and neutralization, anacyl halide by hydrolysis and reaction with a compound such as thionylchloride, nitrites, and others.

[0193] The first and/or second polymers, and/or third polymers in someinstances, have the following characteristics in various combinationsthat separates them from other copolymers made from the same monomers.These characteristics are:

[0194] the ratio of first branches wherein n is 0 to first brancheswherein n is 1 is about 3.0 or more, preferably about 4.0 or more;

[0195] the ratio of first branches wherein n is 0 to first brancheswherein n is 3 is 1.0 or more, preferably 1.5 or more;

[0196] the ratio of second branches wherein m is 0 to second brancheswherein m is one or more is at least about 3.0, more preferably at leastabout 5.0;

[0197] the total number of first branches where n is 0, 1, 2 and 3 insaid polymer is about 10 or more per 1000 CH₂ groups, preferably about20 or more;

[0198] the incorporation of repeat units derived from H₂C═CHC(O)R³³ is0.3 mole percent or more based on the total repeat units derived fromethylene and H₂C═CHC(O)R³³, preferably about 0.5 mole percent or more,especially preferably 1.1 mole percent or more, and very preferablyabout 1.5 mole percent or more (if there are repeat units in which R³³varies, the total of such units shall be used);

[0199] the polymers have end groups of the formula˜˜˜˜˜˜˜—HC═CH—C(O)—R³² and at least about 5 mole percent, preferably atleast about 10 mole percent, of said monomer incorporated is present insaid polymer as end groups of the formula ˜˜˜˜˜˜˜HC═CH—C(O)—R³³, wherein˜˜˜˜˜˜˜ is the remainder of the polymer chain of said end group (thepolymer chain the end group is attached to); and/or

[0200] the said unsaturated end groups are at least 0.001 mole percent,preferably at least about 0.01 mole percent, and more preferably atleast 0.1 mole percent, of the total repeat units (ethylene and polarcomonomer(s)) in said polymer.

[0201] In these polymers any number of these characteristics can becombined as features of these polymers, including the preferredcharacteristics.

[0202] The first, second and third polymers may also contain “saturated”end groups of the formula ˜˜˜˜˜˜C(O)R³³, which with present analyticaltechniques may be indistinguishable from second branches where m is ≧5.In some instances end groups may have the formula ˜˜˜˜˜˜CH═CH₂ (a vinylend group). Such end groups may sometimes be polymerizable, andtherefore polymers with such end groups may be useful as macromonomers.

[0203] It is difficult, and sometimes not possible, to distinguishbetween ester groups which are saturated polymer ends (no olefin bondassociated with the end group), and ester groups at the ends of longbranches by ¹³C NMR spectroscopy (created by chain walking event, aCWE). In both cases the carbonyl group is shifted from about 175.5 ppmfor the inchain comonomer to 170-174 ppm for the saturated end group orCWE. Usually the saturated ester end group or CWE peak in the region170-174 ppm is very small and present in only trace quantities. Becauseof the very low levels of this peak, it is difficult to confirm by 2DNMR this hypothesis, and the assignment should be considered tentative.Review of many of the experimental results obtained show that in manyexamples no saturated end groups and/or CWE are present. However in someexamples up to 50 mole percent, more commonly up to 20 mole percent, ofthe total amount of acrylate ester appears to be present as saturatedend groups and/or CWE. These numbers are very approximate, since thecontents of the saturated end groups and/or CWE are typically so smallthe error in the measurement is relatively large.

[0204] Some NMR and separations evidence exists that these copolymersmay sometimes be capped by short runs of acrylate homopolymers,presumably by free radical polymerization of acrylate ester at thebeginning and/or end of the coordination polymerization of a polymerchain.

[0205] The first, second and third polymers are useful in many ways, forinstance,

[0206] 1. Tackifiers for low strength adhesives (U, vol. A1, p. 235-236)are a use for these polymers. Elastomeric and/or relatively lowmolecular weight polymers are preferred.

[0207] 2. The polymers are useful as base resins for hot melt adhesives(U, vol. A1, p. 233-234), pressure sensitive adhesives (U, vol. A1, p.235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives. The polymers may also be used in a carpetinstallation adhesive.

[0208] 3. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

[0209] 4. The polymers, particularly elastomers, may be used formodifying asphalt, to improve the physical properties of the asphaltand/or extend the life of asphalt paving, see U.S. Pat. No. 3980598.

[0210] 5. Wire insulation and jacketing may be made from any of thepolymers (see EPSE, vol. 17, p. 828-842). In the case of elastomers itmay be preferable to crosslink the polymer after the insulation orjacketing is formed, for example by free radicals.

[0211] 6. The polymers, especially the branched polymers, are useful asbase resins for carpet backing, especially for automobile carpeting.

[0212] 7. The polymers may be used for extrusion or coextrusion coatingsonto plastics, metals, textiles or paper webs.

[0213] 8. The polymers may be used as a laminating adhesive for glass.

[0214] 9. The polymers are useful for blown or cast films or as sheet(see EPSE, vol. 7 p. 88-106; ECT4, vol. 11, p. 843-856; PM, p. 252 andp. 432ff). The films may be single layer or multilayer, the multilayerfilms may include other polymers, adhesives, etc. For packaging thefilms may be stretch-wrap, shrink-wrap or cling wrap. The films areuseful for many applications such as packaging foods, geomembranes andpond liners. It is preferred that these polymers have somecrystallinity.

[0215] 10. The polymers may be used to form flexible or rigid foamedobjects, such as cores for various sports items such as surf boards andliners for protective headgear. Structural foams may also be made. It ispreferred that the polymers have some crystallinity. The polymer of thefoams may be crosslinked.

[0216] 11. In powdered form the polymers may be used to coat objects byusing plasma, flame spray or fluidized bed techniques.

[0217] 12. Extruded films may be formed from these polymers, and thesefilms may be treated, for example drawn. Such extruded films are usefulfor packaging of various sorts.

[0218] 13. The polymers, especially those that are elastomeric, may beused in various types of hoses, such as automotive heater hose.

[0219] 14. The polymers may be used as reactive diluents in automotivefinishes, and for this purpose it is preferred that they have arelatively low molecular weight and/or have some crystallinity.

[0220] 15. The polymers can be converted to ionomers, which when theypossess crystallinity can be used as molding resins. Exemplary uses forthese ionomeric molding resins are golf ball covers, perfume caps,sporting goods, film packaging applications, as tougheners in otherpolymers, and usually extruded) detonator cords.

[0221] 16. The functional groups on the polymers can be used to initiatethe polymerization of other types of monomers or to copolymerize withother types of monomers. If the polymers are elastomeric, they can actas toughening agents.

[0222] 17. The polymers can act as compatibilizing agents betweenvarious other polymers.

[0223] 18. The polymers can act as tougheners for various otherpolymers, such as thermoplastics and thermosets, particularly if theolefin/polar monomer polymers are elastomeric.

[0224] 19. The polymers may act as internal plasticizers for otherpolymers in blends. A polymer which may be plasticized is poly(vinylchloride).

[0225] 20. The polymers can serve as adhesives between other polymers.

[0226] 21. With the appropriate functional groups, the polymers mayserve as curing agents for other polymers with complimentary functionalgroups (i.e., the functional groups of the two polymers react with eachother).

[0227] 22. The polymers, especially those that are branched, are usefulas pour point depressants for fuels and oils.

[0228] 23. Lubricating oil additives as Viscosity Index Improvers formultigrade engine oil (ECT3, Vol 14, p. 495-496) are another use.Branched polymers are preferred. Ethylene copolymer with acrylates orother polar monomers will also function as Viscosity Index Improvers formultigrade engine oil with the additional advantage of providing somedispersancy.

[0229] 24. The polymers may be used for roofing membranes.

[0230] 25. The polymers may be used as additives to various moldingresins such as the so-called thermoplastic olefins to improve paintadhesion, as in automotive uses.

[0231] 26. A flexible pouch made from a single layer or multilayer film(as described above) which may be used for packaging various liquidproducts such as milk, or powder such as hot chocolate mix. The pouchmay be heat sealed. It may also have a barrier layer, such as a metalfoil layer.

[0232] 27. A wrap packaging film having differential cling is providedby a film laminate, comprising at least two layers; an outer reversewhich is a polymer (or a blend thereof) described herein, which containsa tackifier in sufficient amount to impart cling properties; and anouter obverse which has a density of at least about 0.916 g/mL which haslittle or no cling, provided that a density of the outer reverse layeris at least 0.008 g/mL less than that of the density of the outerobverse layer. It is preferred that the outer obverse layer is linearlow density polyethylene, and the polymer of the outer obverse layerhave a density of less than 0.90 g/mL. All densities are measured at 25°C.

[0233] 28. Fine denier fibers and/or multifilaments. These may be meltspun. They may be in the form of a filament bundle, a non-woven web, awoven fabric, a knitted fabric or staple fiber.

[0234] 29. A composition comprising a mixture of the polymers herein andan antifogging agent. This composition is especially useful in film orsheet form because of its antifogging properties.

[0235] 30. If the polymers are functionalized with monomers such asfluoroalkyl acrylate esters or other fluorine-containing monomers, theyare useful for selectively imparting surface activity to polyolefins.This would be of use reducing fluid penetration in flash-spun polyolefinfilms for medical and other applications. The fluoro-functionalizedpolyolefins would also be useful for dispersing fluoropolymers inlubricant applications.

[0236] 31. Mixtures of ethylene homopolymers or oligomers together withcopolymers of ethylene and acrylates and optionally other monomers areuseful as adhesion promoters, surface active agents, tougheners, andcompatibilizers for additives.

[0237] In the above use listings, sometimes a reference is given whichdiscusses such uses for polymers in general. All of these references arehereby included by reference. For the references, “U” refers to W.Gerhartz, et al., Ed., Ullmann's Encyclopedia of Industrial Chemistry,5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which the volume andpage number are given, “ECT3” refers to the H. F. Mark, et al., Ed.,Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley &Sons, New York, “ECT4” refers to the J. I Kroschwitz, et al., Ed.,Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley &Sons, New York, for which the volume and page number are given, “EPSE”refers to H. F. Mark, et al., Ed., Encyclopedia of Polymer Science andEngineering, 2nd Ed., John Wiley & Sons, New York, for which volume andpage numbers are given, and “PM” refers to J. A. Brydson, ed., PlasticsMaterials, 5th Ed., Butterworth-Heinemann, Oxford, UK, 1989, and thepage is given.

[0238] In the Examples, all pressures are gauge pressures. The followingabbreviations are used:

[0239] ΔHf—heat of fusion (in J/g)

[0240] BAF—tetrakis(bis-3,5-(trifluoromethyl)phenyl)borate

[0241] DSC—differential scanning calorimetry

[0242] GPC—gel permeation chromatography

[0243] PMAO-IP—improved processing methylaluminoxane from Akzo-Nobel

[0244] RB—round-bottomed

[0245] RT—room temperature

[0246] TCB—1,2,4-trichlorobenzene

[0247] THF—tetrahydrofuran

[0248] Am—amyl

[0249] Ar—aryl

[0250] BAF—tetrakis(3,5-trifluoromethylphenyl)borate

[0251] BArF—tetrakis(pentafluorophenyl)borate

[0252] BHT—2,6-di-t-butyl-4-methylphenol

[0253] Bu—butyl

[0254] Bu₂O—dibutyl ether

[0255] CB—chlorobenzene

[0256] Cmpd—compound

[0257] E—ethylene

[0258] EG—end-group, refers to the ester group of the acrylate beinglocated in an unsaturated end group of the ethylene copolymer

[0259] EGPEA—2-phenoxyethyl acrylate

[0260] Eoc—end-of-chain

[0261] Equiv—equivalent

[0262] Et—ethyl

[0263] Et_(SBU)—percent of ethyl branches occurring in sec-butyl endedbranches

[0264] GPC—gel permeation chromatography

[0265] HA—hexyl acrylate

[0266] Hex—hexyl

[0267] IC—in-chain, refers to the ester group of the acrylate beingbound to the main-chain of the ethylene copolymer

[0268] IDA—isodecyl acrylate

[0269] Incorp—incorporation

[0270] i-Pr—iso-propyl

[0271] M.W.—molecular weight

[0272] MA—methyl acrylate

[0273] Me—methyl

[0274] MeOH—methanol

[0275] Me_(SBu)—percent of methyl branches occurring in secbutyl endedbranches

[0276] MI—melt index

[0277] Mn—number average molecular weight

[0278] Mp—peak average molecular weight

[0279] Mw—weight average molecular weight

[0280] N:—not determined

[0281] PDI—polydispersity; Mw/Mn

[0282] PE—polyethylene

[0283] Ph—phenyl

[0284] Press—pressure

[0285] RI—refractive index

[0286] Rt or RT—room temperature

[0287] t-Bu—t-butyl

[0288] TCB—1,2,4-trichlorobenzene

[0289] Temp—temperature

[0290] THA—3,5,5-trimethylhexyl acrylate

[0291] THF—tetrahydrofuran

[0292] TO—number of turnovers per metal center=(moles monomer consumed,as determined by the weight of the isolated polymer or oligomers)divided by (moles catalyst)

[0293] tol—toluene

[0294] Total Me—Total number of methyl groups per 1000 methylene groupsas determined by ¹H or ¹³C NMR analysis

[0295] UV—ultraviolet

EXAMPLES 1-89 Ligand Precursor and Catalyst Synthesis

[0296] All operations related to the catalyst synthesis were performedin a nitrogen drybox or using a Schlenk line with nitrogen protection.Anhydrous solvents were used in all cases. Solvents were distilled fromdrying agents under nitrogen using standard procedures: chlorobenzenefrom P₂O₅; THF from sodium benzophenone ketyl. Ni[II] allyl chloride andNaBAF were prepared according to the literature.

[0297] (Tert-butyl)₂PCH₂Li was synthesized by reacting (tert-butyl)₂PCH₃with tert-butyl lithium in heptane in a 109° C. bath for a few hours.The product was filtered and washed with pentane. (Tert-butyl)₂PLi wassynthesized by reacting (tert-butyl)₂PH with n-butyl lithium in heptaneat 90° C. for 6 h. Ph₂Pli was made by reacting Ph₂PH with n-butyllithium at RT for 3 d at RT. The NMR spectra were recorded using aBruker 500 MHz spectrometer or a Bruker 300 MHz spectrometer.

[0298] In the Examples 1-89 the following catalysts were used:

Example 1 - Synthesis of Catalyst 1

[0299] In a drybox, 0.50 g (tert-butyl)₂PCH₂Li was mixed with 20 mL THFin a Schlenk flask. It was brought out of the drybox and placed in anice-water bath. One atmosphere of hexafluoroacetone was applied to theflask. The mixture was allowed to stir at 0° C. under 1 atm ofhexafluoroacetone for 1 h. The hexafluoroacetone flow was stopped. Thereaction mixture was allowed to warm up to RT, during which time gasevolution was seen. The mixture was then stirred at RT for 1 h and wastransferred back to the drybox. The THF was evaporated. The product wasdried under full vacuum overnight. A yellow solid was obtained. ³¹PNMRin THF-d₈: singlet peak at 13.07 ppm. ¹HNMR in THF-d₈: 2.08 ppm (2H, d,JPH=4.6 Hz, P—CH₂—); 1.22 ppm (18H, d, JPH=11.2 Hz, —C(CH₃)₃). A smallamount of THF (˜0.2 eq) existed in the solid product. To this productwas added 0.405 g ((allyl)NiCl)₂ and 15 mL THF. The mixture was allowedto stir at RT over the weekend. The mixture was evaporated to dryness,extracted with 30 mL toluene, filtered through Celite®, followed by 3×5mL toluene wash. Solvent was evaporated. The product was dried underfull vacuum overnight. The product became powdery after triturating withpentane. Yellow brown solid (0.82 g) was obtained. ³¹PNMR in CD₂Cl₂:singlet peak at 78.81 ppm.

Example 2 - Synthesis of catalyst 2

[0300] A 100-mL round-bottomed flask was charged with 292 mg (1.60 mmol)of benzophenone dissolved in ca. 15 mL THF. Then the (t-Bu)₂P—CH₂Li (266mg, 1.60 mmol) dissolved in ca. 15 mL THF was added. The solution turnsfrom colorless to dark blue. It was stirred for one hour after whichtime, a solution of (Ni(C₃H₅)Cl)₂ (217 mg, 0.80 mmol) in 15 mL THF wasadded. It was stirred for an additional 1 h and the solvent removed. Theresidue was extracted with hexane and toluene and the solvent removed.The residue was washed with small amounts of hexane and dried. The yieldwas 395 mg (71%). ¹HNMR (CD2Cl2, 23° C., 300 MHz) d 8.2-7.9 (m, 4H, Ar);7.4-6.9 (m, 6H, Ar); 5.10 (m, 1H); 4.26 (brs, 1H); 3.25 (dd, J=14 Hz,J=5 Hz, 1H), 2.80 (m, 2H), 2.24 (brs, 1H), 1.16 (d, J=13 Hz, 1H), 0.97(d, JP—H=13 Hz, 9H); 0.80 (d, JP—H=13 Hz). ³¹PNMR (CD2Cl2, 23° C.,): d84.0. ¹³CNMR (CD2Cl2, 23° C., 75 MHz) d 156.1 (s); Ar C—H signalsoverlapping with C6D6 signal; 127.2 (s); 125.7 (d, JP—C=6 Hz); 109.3 (d,JC—H=157 Hz); 86.7 (d, JP—C=10 Hz); 69.1 (m, JP—C=22 Hz); 41.2 (dt,JP—C=25 Hz, JC—H=127 Hz); 37.6 (m, JP—C=6 Hz); 33.8 (m); 29.9 (q,JC—H=124 Hz).

[0301] A single red-orange crystal was grown from CH₂Cl₂/hexane atambient temperature, and X-ray diffraction data confirmed the structure.No LiCl was present in the structure based X-ray single crystaldiffraction analysis.

Example 3 - Synthesis of catalyst 3

[0302] In a drybox, 0.2273 g (tert-butyl)₂PCH₂Li was mixed with 20 mLTHF in a 100 mL RB flask. The mixture was cooled at −30° C. for 30 min.Under stirring, 0.50 g monoimine-A was added to the solution while thesolution was still cold. The reaction mixture turned yellow blue rightaway. The mixture was allowed to warm up to RT and to stir at thistemperature overnight. THF was evaporated. The product was dried undervacuum for 7 h. A deep yellow green solid (0.912 g) was isolated. ³¹PNMRin THF-d₈: singlet peak at 18.56 ppm. To the product was added 0.1847 g((allyl)NiCl)₂ and 20 mL THF in a RB flask. The mixture was allowed tostir for 6.5 h at RT. The mixture was evaporated to dryness. The residuewas extracted with 25 mL toluene. It was filtered through Celite®,followed by 3×5 mL toluene wash. The solution was evaporated to dryness.The product was then dried under full vacuum overnight. Dark green solid(0.92 g) was isolated.

Example 4 - Synthesis of Catalyst 4

[0303] In a drybox, 0.35 g (tert-butyl)₂PCH₂Li was added to the −30° C.solution of 0.4409 g monoimine-B in 30 mL THF in a 100 mL RB flask. Thereaction mixture turned yellow blue immediately. The mixture was allowedto warm up to RT and stirred at this temperature for 19 h. THF wasevaporated. The product was dried under vacuum. ³¹PNMR in THF-d₈: Twosinglet peaks. One was a sharp and tall peak at 20.54 ppm and anotherwas a wide and short peak at 18.74 ppm. To the product was added 0.2812g ((allyl)NiCl)₂ and 30 mL THF in a RB flask. The mixture was allowed tostir for 18 h at RT. The mixture was evaporated to dryness. The residuewas extracted with 30 mL toluene. It was filtered through Celite®,followed by 3×5 mL toluene wash. The solution was evaporated to dryness.The solid product was then dried under vacuum for 8 h. ³¹PNMR in C₆D₆:two major singlet peak at 81.75 ppm and 79.92 ppm, as well as a minorsinglet peak at 20.05 ppm. Electron spray mass spectroscopy showed majorpeaks at 468 and 470 (due to ⁵⁸Ni and ⁶⁰Ni isotopes), which indicatedthat the desired product picked up a proton in the spray process. X-raysingle crystal diffraction analysis confirmed the structure. No LiCl waspresent in the structure.

Examples 5 - Synthesis of Catalyst 5

[0304] A 100 mL RB flask was charged with 217 mg (0.82 mmol) of2,2,2-trifluoro-2′,4′,6′-trimethoxyacetophenone dissolved in ca. 10-15mL THF. Then (t-Bu)₂P—CH₂Li (136 mg, 0.82 mmol) dissolved in ca. 10-15mL THF was added. The initially purple solution (color came from tracesimpurities in starting ketone) turned clear yellow. It was stirred forone h after which time, a solution of (Ni(C₃H₅)Cl)₂ (111 mg, 0.41 mmol)in 10-15 mL THF was added. It was stirred for an additional one h andthe solvent removed. The residue was washed with hexane and dried invacuo to yield 362 mg (78%). Key NMR signals (incomplete): ¹H-NMR(CD₂Cl₂, 23° C., 300 MHz) δ 6.5-6.2 (brm, 2H, Ar); 5.3 (brm, 1H), 4.8(brs, 1H); 4.1 (brs, 2H); 3.8 (brs, 9H); 3.7-2.0 (brm); 2.0-0.8 (brm,t-Bu signals). Two isomers (50:50) by ³¹PNMR (CD₂Cl₂, 23° C., 300 MHz):δ 81.4; 80.2. ¹³CNMR (CD₂Cl₂, 23° C., 125 MHz): δ 161.3 (s); ca. 112(brs); ca. 94.0 (brm, J=158 Hz); 93.2 (br); ca. 86; 68.1; 58.4; 56.3;55.6. A single red-orange crystal was grown from CH₂Cl₂/hexane atambient temperature, and the structure confirmed by X-ray diffraction.The complex contained one equivalent of LiCl, and existed as a dimerbridged by LiCl.

Example 6 - Synthesis of Catalyst 6

[0305] A 200 mL RB flask was charged with 300 mg (1.10 mmol) of2,4,6-trimethoxybenzophenone dissolved in ca. 20 mL THF. Then(t-Bu)₂P—CH₂Li (183 mg, 1.10 mmol) dissolved in ca. 20 mL THF was added.It was stirred for one h, after which time, a solution of (Ni(C₃H₅) Cl)₂(149 mg, 0.55 mmol) in THF (ca. 20 mL) was added. It was stirred for anadditional one h and the solvent removed. The residue was washed withhexane and dried in vacuo to yield 664 mg product. Key NMR signals(incomplete) : ¹HNMR (CD₂Cl₂, 23° C., 300 MHz) δ 7.64 (brs, 1H, Ar);7.51 (brs, 1H, Ar); 7.14 (brt, 2H, Ar); 7.00 (brt, 1H, Ar); 6.14 (s,2H); 5.28 (m, 1H); 5.0-4.5 (brm, 2H) ; 3.67 (s, 3H, OCH3) ; 3.64 (s, 6H,OCH₃) ; 3.26 (brs, 1H) 2.87 (dd, 1H, J=14 Hz, J=5 Hz); 2.8-2.4 (brm,2H); 1.7-0.7 (brm, 18H, t-Bu). Two isomers (50:50) by ³¹PNMR (CD₂Cl₂,23° C., 75 MHz): δ 79.0; 78.2. ¹³CNMR (CD₂Cl₂, 23° C., 125 MHz): δ 167.9(d, J_(P-C)=4.5 Hz); 159.9 (s); 158.5 (brs); 154.4 (brs); 127.6 (dd,J_(C-H)=158 Hz, J=7.5 Hz); 126.1 (dt); 125.7 (dt, J=150 Hz); 111.0(brd); 95.0 (dd, J_(C-H)=159 Hz, J=4.7 Hz); 87.2 (brs); 67.0 (brdt,J_(P-C)=22 Hz); 57.7 (q, J_(C-H)=145 Hz); 55.6 (q, J_(C-H)=144 Hz); ca.40.0 (brs); 39.7 (dt, J_(P-C)=25 Hz); 35.3 (d, J_(P-C)=18 Hz); 33.7 (d,J_(P-C)=16 Hz); 30.0 (brq, J_(C-H)=127 Hz). A single red-orange crystalwas grown from CH₂Cl₂/hexane at ambient temperature, and an X-raydiffraction confirmed the structure. The complex contained oneequivalent of LiCl, and existed as a dimer bridged by LiCl.

Example 7 - Synthesis of Catalyst 7

[0306] A 200 mL RD flask was charged with 300 mg(1.17 mmol) of2,2-dimethoxy-2-phenylacetophenone dissolved in ca. 20 mL THF. Then(t-Bu)₂P—CH₂Li (195 mg, 1.17 mmol) dissolved in ca. 20 mL THF was added.It was stirred for one h, after which time a solution of (Ni(C₃H₅)Cl)₂(158 mg, 0.59 mmol) in THF (ca. 20 mL) was added. It was stirred for anadditional h and the solvent removed. The residue was washed with hexaneand dried in vacuo to yield 438 mg (67%). Two isomers (50:50) by ³¹PNMR(CD₂Cl₂, 23° C., 300 MHz) : δ 82.1 (s) and δ 81.5 (s). A singlered-orange crystal was grown from CH₂Cl₂/hexane at ambient temperature,and X-ray diffraction data confirmed the structure. The complexcontained one equivalent of LiCl, and existed as a dimer bridged byLiCl.

Example 8 - Synthesis of Catalyst 8

[0307] In a drybox, 0.3043 g (tert-butyl)₂PLi was added to a −30° C.solution of 0.5284 g 2,2,2-trifluoro-2′,4′,6′-trimethoxyacetophenone(Aldrich) in 15 mL THF in a 100 mL RB flask. The reaction mixture turnedyellow. The mixture was allowed to warm up to RT and stir at thistemperature overnight. THF was evaporated. The product was dried undervacuum for 6 h. ³¹PNMR in THF-d₈: a singlet peak at 41.28 ppm. Theproduct was mixed with 0.1608 g ((allyl)NiCl)₂ and 15 mL THF in a RBflask. The mixture was allowed to stir for 2 h at RT. It was thenevaporated to dryness. The residue was mixed with 10 mL toluene. Pentane(40 mL) was then added into the flask. The brown solid was filtered,followed by 3× pentane wash and dried in vacuo. Brown solid (0.445 g)was obtained. ³¹PNMR in THF-d₈: two singlet peak at 50.31 ppm and 50.05ppm.

Example 9 - Synthesis of Catalyst 9

[0308] In a drybox, 0.30 g (tert-butyl)₂PCH₂Li was added to a −30° C.solution of 0.3072 g ethyl trifluoropyruvate (Lancaster) in 15 mL THF ina 100 mL RB flask. The reaction mixture turned golden yellow. Themixture was allowed to warm up to RT and stir at this temperature for 1h. THF was evaporated. The product was dried under vacuum overnight. Theproduct was mixed with 0.247 g ((allyl)NiCl)₂ and 15 mL THF in a RBflask. The mixture was allowed to stir for 1 h at RT. The mixture wasthen evaporated to dryness. The residue was dissolved by adding 10 mLtoluene. Pentane (40 mL) was then added into the flask. The yellow solidwas filtered, followed by 3× pentane wash and dried in vacuo. Yellowsolid (0.36 g) was obtained. ³¹PNMR in THF-d₈: The major singlet peak at78.24 ppm and two small singlet peaks at 96.72 ppm and 218.21 ppm. Asingle crystal was grown and the structure was confirmed synchrotrondiffraction analysis. The complex contained one equivalent of LiCl, andexisted as a dimer bridged by LiCl.

Example 10 - Synthesis of Catalyst 10

[0309] In a drybox, 0.502 g (tert-butyl)₂PLi was added to a −30° C.solution of 0.5613 g ethyl trifluoropyruvate (Lancaster) in 25 mL THF ina 100 mL RB flask. The reaction mixture turned yellow and then coppercolor. The mixture was allowed to warm up to RT and to stir at thistemperature overnight. THF was evaporated. The product was dried undervacuum. ³¹PNMR in THF-d₈: singlet peak at 41.22 ppm. The product wasmixed with 0.453 g ((allyl)NiCl)₂ and 25 mL THF in a RB flask. Themixture was allowed to stir for 1 h at RT. The mixture was evaporated todryness. The residue was mixed with 5 mL toluene. Pentane (40 mL) wasthen added into the flask. The brown solid was filtered, followed by 3×pentane wash and dried in vacuo. Brown solid (0.745 g) was obtained³¹PNMR in THF-d₈: Singlet peak at 46.04 ppm.

Example 11 - Synthesis of Catalyst 11

[0310] In a drybox, 0.40 g Ph₂PLi was added to a −30° C. solution of0.4357 g monoimine-B in 25 mL THF in a 100 mL RB flask. The reactionmixture turned orange. The mixture was allowed to warm up to RT and stirat this temperature for 1 h. THF was evaporated. The product was driedunder vacuum. ³¹PNMR in THF-d₈: A major singlet peak at −22.60 and twosmall singlet peaks at −16.15 ppm and −82.25 ppm. The product was mixedwith 0.2798 g ((allyl)NiCl)₂ and 25 mL THF in a RB flask. The mixturewas allowed to stir for 2 h at RT. The mixture was evaporated todryness. The residue was extracted with toluene, filtered and washedwith toluene. Solvent was evaporated. The product was dried in vacuo.

Example 12 - Synthesis of Catalyst 12

[0311] In a drybox, 0.40 g Ph₂PLi was added to a −30° C. solution of0.3794 g benzophenone in 25 mL THF in a 100 mL RB flask. The reactionmixture turned blue-green. The mixture was allowed to warm up to RT andto stir at this temperature for 1 h. THF was evaporated. The product wasdried under vacuum. ³¹PNMR in THF-d₈: A major singlet peak at −14.28 anda small singlet peaks at −26.30 ppm, as well as a tiny singlet peak at−39.62 ppm. The product was mixed with 0.2796 g ((allyl)NiCl)₂ and 25 mLTHF in a RB flask. The mixture was allowed to stir for 2 h at RT. Themixture was evaporated to dryness. The residue was extracted withtoluene, filtered and washed with toluene. Solvent was evaporated. Theproduct was dried in vacuo.

Example 13 - Synthesis of Catalyst 13

[0312] In a drybox, 0.30 g (tert-butyl)₂PCH₂Li was added to a −30° C.solution of 0.5137 g 4,4′-bis(dimethylamino)thio-benzophenone in 20 mLTHF in a 100 mL RB flask. The reaction mixture turned golden yellow. Themixture was allowed to warm up to RT and to stir at this temperature fora few h. THF was evaporated. The product was dried under vacuumovernight. ³¹PNMR in THF-d₈: A major singlet peak at 21.53 ppm and someminor peaks at 26.05 ppm, 24.34 ppm, 16.58 ppm and 12.74 ppm. Theproduct was mixed with 0.148 g ((allyl)NiCl)₂ and 15 mL THF in a RBflask. The mixture was allowed to stir for 2 h at RT. The mixture wasevaporated to dryness. The solid product was dried in vacuo overnight.³PNMR in THF-d₈: A singlet peak at 101.84 ppm.

Example 14 - Synthesis of Catalyst 14

[0313] In a drybox, 0.40 g (tert-butyl)₂PCH₂Li was added to a −30° C.solution of 0.2485 g benzonitrile in 20 mL THF in a 100 mL RB flask. Thereaction mixture turned red-orange. The mixture was allowed to warm upto RT and stir at this temperature for a few hours. THF was evaporated.The product was dried under vacuum overnight. ³¹PNMR in THF-d₈: A broadsinglet peak at 7.26 ppm. ¹HNMR in THF-d₈ indicated that it was(t-Bu)₂PCH(Li)C(Ph)═NH: 1.14 ppm (18H, (CH₃)₃C—, d, ³JPH=10.8Hz); 3.71ppm (1H, broad singlet); 4.23 ppm (1H, broad singlet, —C(Ph)═NH); 7.11ppm (1H, ArH, t); 7.18 ppm (2H, ArH, t); 7.64ppm (2H, ArH, d). Theproduct was mixed with 0.327 g ((allyl)NiCl)₂ and 20 mL THF in a RBflask. The mixture was allowed to stir for 2.5 h at RT. The mixture wasevaporated to dryness. The solid product was extracted with 10 mLtoluene and was filtered through Celite®, followed by 3×10 mL toluenewash. Toluene was evaporated. The solid product was dried in vacuoovernight. Dark brown solid (0.379 g) was obtained. ³¹PNMR in THF-d₈: Asinglet peak at 73.06 ppm. ¹HNMR in THF-d₈ indicated that it is theexpected ((t-Bu)₂PCH₂C(Ph)═NNi(allyl)) complex: 1.26 and 1.41 ppm (9Heach, (CH₃)₃C—, d, ³JPH=12.9 Hz for both); 1.59 and 2.49 ppm (1H each,d, PCHH′); 3.11, 3.59, 3.68, 4.24 ppm (1H each, broad singlets,allyl-H); 5.02 ppm (1H, m, central allyl-H); 7.26 ppm (3H, s, ArH); 7.53ppm (2H, s, ArH).

Example 15 - Synthesis of Catalyst 15

[0314] In a drybox, 0.40 g (tert-butyl)₂PLi was added to a −30° C.solution of 0.2186 g trimethylacetonitrile in 20 mL THF in a 100 mL RBflask. The reaction mixture turned yellow. The mixture was allowed towarm up to RT and to stir at this temperature for 3 d. THF wasevaporated. The product was dried under vacuum overnight. ³¹PNMR inTHF-d₈: 45.93 ppm and a minor peak at 21.13 ppm. The product was mixedwith 0.357 g ((allyl)NiCl)₂ and 20 mL THF in a RB flask. The mixture wasallowed to stir for 1 h at RT. The mixture was evaporated to dryness.The solid product was extracted with toluene and was filtered throughCelite®, followed by 3× toluene wash. Toluene was evaporated. The solidproduct was dried in vacuo overnight. Red-brown solid (0.476 g) wasobtained.

Example 16 - Synthesis of Catalyst 16

[0315] In a drybox, 0.40 g (tert-butyl)₂PCH₂Li was added to a −30° C.solution of 0.2003 9 trimethylacetonitrile in 20 mL THF in a 100 mL RBflask. The reaction mixture turned yellow. The mixture was allowed towarm up to RT and stir at this temperature for 3 d. THF was evaporated.The product was dried under vacuum overnight. ³¹PNMR in THF-d₈: A majorsinglet peak at 17.67 ppm and a minor peak at 12.78. The product wasmixed with 0.327 g ((allyl)NiCl)₂ and 20 mL THF in a RB flask. Themixture was allowed to stir for 1 h at RT. The mixture was evaporated todryness. The solid product was mixed with 10 mL toluene first and then40 mL pentane. The solid was filtered, followed by 3× pentane wash anddried in vacuo overnight. ³¹PNMR in THF-d₈: A singlet peak at 73.48 ppm.¹HNMR in THF-d₈: 1.18ppm (d, —P(CH₃)₃, 18H); 1.34 ppm (d, —C(CH₃)₃, 9H);1.49ppm, 2.38 ppm (1H each, d, PCHH′); 3.01 ppm, 3.23 ppm, 3.44 ppm,3.97 ppm (1H each, brs, allyl-H); 4.92 ppm (1H, central allyl-H, m).

Example 17 - Synthesis of Catalyst 17

[0316] In a drybox, 0.40 g (tert-butyl)₂PLi was added to a −30° C.solution of 0.5529 g benzil in 20 mL THF in a 100 mL RB flask. Thereaction mixture turned dark red-brown. The mixture was allowed to warmup to RT and stir at this temperature overnight. THF was evaporated. Theproduct was dried under vacuum overnight. ³¹PNMR in THF-d₈: A majorsinglet peak at 41.09 ppm and a minor peak at 2.45 ppm. The product wasmixed with 0.359 g ((allyl)NiCl)₂ and 20 mL THF in a RB flask. Themixture was allowed to stir for 1 h at RT. The mixture was evaporated todryness. The solid product was mixed with 10 mL toluene first and then90 mL pentane. The solid was filtered, followed by 3× pentane wash anddried in vacuo overnight. Light brown solid (0.59 g) was obtained.

Example 18 - Synthesis of Catalyst 18

[0317] In a drybox, 0.40 g (tert-butyl)₂CH₂PLi was added to a −30° C.solution of 0.5066 g benzil in 20 mL THF in a 100 mL RB flask. Thereaction mixture turned dark red-brown. The mixture was allowed to warmup to RT and to stir at this temperature overnight. THF was evaporated.The product was dried under vacuum overnight. ³¹PNMR in THF-d₈: A majorsinglet peak at 14.28 ppm and several minor peaks were observed. Theproduct was mixed with 0.329 g ((allyl)NiCl)₂ and 20 mL THF in a RBflask. The mixture was allowed to stir for 1 h at RT. The mixture wasevaporated to dryness. The solid product was mixed with 10 mL toluenefirst and then 90 mL pentane. The solid was filtered, followed by 3×pentane wash and dried in vacuo overnight. Yellow solid (0.285 g) wasobtained. ³¹PNMR in THF-d₈: A major singlet peak at 94.03 ppm and minorpeaks at 67.51, 66.72 and 62.29 ppm were observed.

Example 19 - Synthesis of Catalyst 19

[0318] A 100 mL RB flask was charged with 102 mg (0.86 mmol) of phenylisocyanate dissolved in ca. 10 mL THF. Then (t-Bu)₂P—CH₂Li (143 mg, 0.86mmol) dissolved in ca. 10 mL THF was added. The solution is clearyellow. It was stirred for one h, after which time a solution of(Ni(C₃H₅)Cl)₂ (116 mg, 0.43 mmol) in 15 mL THF was added. The solutionturned brown-yellow. It was stirred for an additional one h and thesolvent removed. The residue was washed with hexane and dried in vacuo.The yield was 207 mg (57%). Key NMR signals (incomplete) : ¹HNMR(CD₂Cl₂, 23° C., 300 MHz) δ 7.7-6.5 (brm, Ar); 5.32 (brs), 5.09 (m);3.64 (brm); 3.01 (brm); 3.0-2.3 (brm); 2.0-0.6 overlapping signals+twodoublets (J=14 Hz) at 1.42 ppm and 1.27 ppm corresponding to t-Busignals). ³¹PNMR (CD₂Cl₂, 23° C., 300 MHz): δ 50.6.

Example 20A - Synthesis of (t-Bu)₂POC(CH3)₂C(CH₃)₂OH

[0319] In a drybox, 0.623 g pinacol and 2.0 g (t-Bu)₂PCl were dissolvedin 20 mL THF. To this mixture was added over 10 min 0.4438 g KH inportions. The mixture was allowed to stir at RT for 12 d. The mixturewas filtered through Celite®, followed by 3×5 mL THF wash. Solvent wasevaporated. The viscous liquid was dried overnight. Light tan viscousliquid was obtained. ³¹PNMR in CD₂Cl₂: A singlet peak at 135.29 ppm anda few minor peaks. Crystals grew out of the liquid in several days.X-ray single crystal analysis indicated that it was the desired product.It existed as tetramer in the solid state through hydrogen bonding.

Example 20B - Synthesis of Catalyst 20

[0320] Catalyst 20 was generated in-situ by adding 13.9 mg of(t-Bu)₂POC(CH₃)₂C(CH₃)₂OH to a chlorobenzene solution of (TMEDA)NiMe₂(10.2 mg in 5 mL chlorobenzene, TMEDA=tetramethylethylenediamine).

Example 20C - Polymerization using Catalyst 20

[0321] The in-situ prepared Catalyst 20 (0.05 mmol, see Example 20B) wasscreened for ethylene polymerization at 6.9 MPa of ethylene at 50° C.for 18 h in a shaker tube. Polyethylene (0.067 g) was obtained. It hadmelting points of 131° C. (166.7 J/g) and 114° C. (33.5 J/g).

Example 21 - Synthesis of Catalyst 21

[0322] In a drybox, 0.489 g (tert-butyl)₂PCH₂Li was mixed with 25 mL THFin a Schlenk flask. It was brought out of the drybox and placed in anice-water bath. One atmosphere of carbon dioxide was applied to theflask. The mixture was allowed to stir at 0° C. under 1 atm of carbondioxide for 15 min and then at RT for 45 min. The CO₂ flow was stopped.THF was evaporated. The product was dried under full vacuum overnight.Tan yellow solid was obtained. Part of the product (0.4204 g) was mixedwith 0.2704 g ((allyl)NiCl)₂ in 20 mL THF. The mixture was allowed tostir at RT for 40 min. The mixture was evaporated to dryness and wasadded to 5 mL toluene to dissolve, followed by addition of about 70 mLpentane. The solid was filtered, followed by 3×5 mL pentane wash. Theproduct was dried under full vacuum overnight. Orange solid (0.48 g) wasobtained. ³¹PNMR in THF-d₈: singlet peak at 51.70 ppm. ¹HNMR in THF-d₈:5.34 ppm (bm, central allyl-H, 1H); 2.67-2.95 (bm, allyl-CH₂ andPCH₂-6H) ; 1.34 ppm (d, J_(PH)=12.4Hz, C(CH₃)₃, 18H) . Lithium NMR inC₆D₆ of 21 and a crystal structure of the Zwitterion tetrafluoroboratederivative indicate that one equivalent of Li⁺ present which canpotentially complex to 21 does not in fact complex to 21.

Example 22 - Synthesis of Catalyst 22

[0323] In a drybox, 0.1009 g (tert-butyl)₂PCH₂C(Ph)₂OLi^(·)THF (seeExample 2) was dissolved in 5 mL THF in a 20 mL vial. To this was added56 mg of ZrCl₄. The solution turned a peach color. It was allowed tostir overnight. Solvent was evaporated and the resulting solid was driedin vacuo.

Example 23 - Synthesis of Catalyst 23

[0324] In a drybox, 0.1009 g (tert-butyl)₂PCH₂C(Ph)₂OLi^(·)THF (seeExample 2) was dissolved in 5 mL THF in a 20 mL vial. To this was added45.5 mg of TiCl₄. The solution turned dark amber. It was stirredovernight. Solvent was evaporated and the resulting tan solid was driedin vacuo.

Ethylene Polymerization Screening Using the Nickel Catalysts 1-21

[0325] In a drybox, a glass insert was loaded with the isolated Nicatalysts (except Catalyst 20 in Example 20, which was generatedin-situ). Solvent (TCB or chlorobenzene), optionally comonomers wereadded to the glass insert. A Lewis acid cocatalyst (typically BPh₃ orB(C₆F₅)₃) was often added to the solution. The insert was then cappedand sealed. Outside of the drybox, the tube was placed under ethyleneand was shaken mechanically at desired temperature listed in Table 3 forabout 18 h. Sometimes an aliquot of the solution was used to acquire a¹HNMR spectrum. The remaining portion was added to about 20 mL ofmethanol in order to precipitate the polymer. The polymer was isolated,washed with methanol several times and dried in vacuo.

Ethylene Polymerization Screening by the Catalysts 22 and 23, in thepresence of MAO

[0326] In a drybox, a glass insert was loaded with 0.02 mmol of theisolated Zr or Ti catalyst and 9 mL of 1,2,4-trichlorobenzene. It wasthen cooled to −30° C. PMAO-IP (1 mL 12.9wt % (in Al) toluene solution)was added to the frozen solution. It was put in a −30° C. freezer. Theinsert was then capped and sealed. Outside of the drybox, the cold tubewas placed under ethylene and was shaken mechanically at desiredtemperature listed in Table 3, condition V, for about 18 h. Methanol(about 15 mL) and 2 mL conc. hydrochloric acid was added to the mixture.The polymer was isolated, washed with methanol several times and driedin vacuo.

Polymer Characterization

[0327] The results of ethylene polymerization and copolymerizationcatalyzed by Catalysts 1-23 under different reaction conditions (SeeTable 3) are reported in Tables 4-13. The polymers were characterized byNMR, GPC and DSC analysis. A description of the methods used to analyzethe amount and type of branching in polyethylene is given in previouslyincorporated U.S. Pat. No. 5,880,241. GPC's were run in trichlorobenzeneat 135° C. and calibrated against polyethylene using universalcalibration based on polystyrene narrow fraction standards. DSC wasrecorded between −100° C. to 150° C. at a heating rate of 10° C./min.Data reported here are all based on second heat. ¹HNMR of the polymersamples was run in tetrachloroethane-d₂ at 120° C. using a 500 MHzBruker spectrometer. TABLE 3 Conditions for Ethylene Polymerization andCopolymerization Screening. I 0.02 mmol catalyst, 10 mL TCB, RT, 18 h,6.9 MPa ethylene, 10 eq B(C₆F₅)₃ II 0.02 mmol catalyst, 10 mL TCB, RT,18 h, 1.0 MPa ethylene, 10 eq B(C₆F₅)₃ III 0.02 mmol catalyst, 10 mLTCB, 60° C., 18 h, 1.0 MPa ethylene, 10 eq B(C₆F₅)₃ IV 0.02 mmolcatalyst, 3 mL TCB, 2 mL E-10-U*, 60° C., 18 h, 1.0 MPa ethylene, 40 eqB(C₆F₅)₃ V 0.02 mmol catalyst, 9 mL TCB, 1 mL PMAO-IP (12.9 wt % (in Al)in toluene), RT, 18 h, 6.9 MPa ethylene VI 0.02 mmol catalyst, 4 mL TCB,1 mL n-hexyl acrylate, 120° C., 18 h, 6.9 MPa ethylene, 40 eq B(C₆F₅)₃VII 0.02 mmol catalyst, 10 mL TCB, 60° C., 18 h, 1.0 MPa ethylene, 10 eqB(C₆F₅)₃, 1 eq NaBAF

[0328] TABLE 4 Ethylene Polymerization at 6.4 MPa Ethylene in ShakerTubes (0.05 mmol catalyst, 5 mL chlorobenzene, 18 h) Cocatalyst/ Yield#Me/ m.p. Ex. Catalyst amt T (° C.) (g) 1000CH₂ (° C.) Mw/PDI TON** 24 1BPh₃/5eq 25 10.202 <1 136 (162*) 737,803/3.5  7,287 25 1 B(C₆F₅)₃/5eq 254.764 9 128 134,256/60.2 3,403 26 1 none 25 0 27 1 BPh₃/5eq 80 4.990 6133 47,301/3.3 3,564 28 1 B(C₆F₅)₃/5eq 80 1.710 12 124  15,813/14.01,221 29 2 B(C₆F₅)₃/5eq 80 2.280 31 125  4,759/3.0 1,629 30 2 BPh₃/5eq80 0 31 4 B(C₆F₅)₃/10eq 50 4.862 86 114, 106  28,765/41.8 3,466 32 11B(C₆F₅)₃/10eq 50 0.117 25 119, 102   209 33 12 B(C₆F₅)₃/2eq 50 0.046 19119, 102   82

[0329] TABLE 5 Ethylene (Co)polymerization at 2.1 MPa Ethylene in ShakerTubes (0.05 mmol catalyst, 5 mL solvent/comonomer, 18 h) Cocatalyst/Solvent/ T Yield Mole % #Me/ m.p. Mw/ TON Ex. Catalyst eq Comonomer (°C.) (g) Comonomer 1000CH₂ (° C.) PDI E/Comonomer 34 1 BPh₃/2 C₆H₅Cl 505.518 <1^(a)) 136 173,568/3.1  3941 35 1 BPh₃/5 C₆H₅Cl 50 4.56 2 135191,589/5.1 3,321 36 1 BPh₃/10 C₆H₅Cl 50 5.132 2 137 268,453/3.5 3,66637 1 BPh₃/10 1-Hexene 50 1.295 12  111 121,450/2.4 / 38 1 BPh₃/10 E-4-P*50 4.972 3.0  1^(b)) 117  62,753/3.7 3,100/97 39 2 B(C₆F₅)₃/2 C₆H₅Cl 501.816 8 127  20,100/9.2 1,297 40 2 B(C₆F₅)₃/10 C₆H₅Cl 50 12.314 12   125***  19,712/5.1 8,796 41 2 B(C₆F₅)₃/10 1-Hexene 50 3.662 48^(c)) 99  14,611/5.2 / 42 2 B(C₆F₅)₃/30 E-10-U** 80 5.616 9.9 24  −10 7,298/6.0  2,189/240 43 3 B(C₆F₅)₃/10 C₆H₅Cl 50 1.799 28  113 189,503/16.6 1,285 44 3 BPh₃/10 C₆H₅Cl 50 0 45 3 B(C₆F₅)₃/10 1-Hexene50 0.738 87  72 146,422/3.4 / 46 3 B(C₆F₅)₃/30 E-10-U 80 3.427 2.2 105 117, 106 264,357107.9 2,089/47

[0330] TABLE 6 Ethylene (Co)polymerization 1.0 MPa Ethylene at 50° C. inShaker Tubes (0.05 mmol catalyst, 5 mL solvent/comonomer, 18 hr) TONCocatalyst/ Solvent/ Yield Mole % #Me/ Mw/ E-Co- Ex Catalyst eqComonomer (g) Comonomer 1000CH₂ PDI monomer 47 2 B(C₆F₅)₃/30 MUE* 1.9286.3 11 7,674/3.7 952/64 48 4 B(C₆F₅)₃/30 MUE  0.102 6.0 24 17,303/11.751/3

[0331] TABLE 7 Condition I in Table 3 Cata- Yield #Me/ m.p. Ex lyst (g)1000 CH₂ (° C.)(ΔH_(f)) Mw/PDI TON 49 2 7.264 6 128 (234)  32,932/3.8212,947 50 5 15.560 10 125 (218)  13,921/4.91 27,734 51 6 11.718 14 124(206)  10,411/3.68 20,886 52 7 10.619 20 117 (185)  2,792/2.57 18,927 5313 0.029 7 131 (161)  49,268/4.1 52 54 8 8.970 22 125 (142) 187,705/4.915,988 55 9 9.728 12 130 (194)  30,547/18.3 17,339 56 10 0.112 22 127(182) 190,093/182.7 200 trimodal 57 14 6.401 121 120 (81)   67,779/251.511,409 trimodal 58 15 8.407 16 126 (102)  93,871/3.1 14,985 59 16 0.08873 123 (99)   25,262/24.7 157 60 17 1.250 30 129 (141)  73,164/2.4 222861 18 14.279 33 118 (148)  4,162/4.7 25,450 62 19 11.233 21 121 (169) 14,451/7.0 20,022 63 21 19.292 52 114 (169),  4,593/3.9 34,386 108

[0332] TABLE 8 Condition II in Table 3 Cata- Yield #Me/ m.p. Ex lyst (g)1000 CH₂ (° C.)(ΔH_(f)) Mw/PDI TON 64 2 2.492 19 120 (140) 46,024/4.54,442 65 5 1.202 10 127 (181) 52,542/4.3 2,142 66 6 2.631 30 120 (130)11,521/3.2 4,689 67 7 1.188 21 122 (207)  6,405/3.2 2,117 68 9 2.057 22125 (175) 32,505/37.8 3,666

[0333] TABLE 9 Condition III in Table 3 Cata- Yield #Me/ m.p. Ex lyst(g) 1000 CH₂ (° C.)(ΔH_(f)) Mw/PDI TON 69 2 1.934 11 125 (164)13,263/3.1 3447 70 5 6.624 13 124 (194) 10,468/3.2 11,807 71 6 6.276 30115 (198)  5,285/3.6 11,186 72 7 4.196 32 115 (172)  2,688/2.6 7,479 7318 5.629 38 108 (88)   8,381/9.1 10,033 74 19 9.868 50 100 (63)  7,784/9.8 17,589 75 21 6.560 31 113 (112)  5,581/5.5 11,692

[0334] TABLE 10 Condition IV in Table 3 Mole % m.p. Cata- Yield #Me/Comon- (° C.) Mw/ TON Ex lyst (g) 1000CH₂ omer (ΔH_(f)) PDI E/EU* 76 20.648 6 2.8 112 5,737/ 947/ (124) 2.6 28 77 5 3.861 6 4.9 108 6,315/4,939/ (92) 2.5 257 78 6 0.129 12 5.1 124, 7,435/ 164/ 108 4.0 9 (124)79 7 0.268 16 4.8 88 1,665/ 347/ (116) 2.9 17 80 15 0.060 15 2.6 11429,070/ 89/ (132) 6.8 2 81 18 2.360 11 15.0 3,017/ 1,798/ 2.5 318 82 191.165 21 10.6 7,057/ 1,095/ 4.0 130

[0335] TABLE 11 Condition V in Table 3 Cata- Yield #Me/ m.p. Ex lyst (g)1000 CH₂ (° C.)(ΔH_(f)) TON 83 22 5.50 21 132 (157) 9,803 84 23 4.520 18134 (136) 8,056 85 23* 4.543 8 134 (125) 8,097

[0336] TABLE 12 Condition VI in Table 3 Mole % m.p. Cata- Yield #Me/Comon- (° C.) Mw/ TON Ex lyst (g) 1000CH₂ omer (ΔH_(f)) PDI E/HA 86 2114.07 27 0.74* 114 2,757/ 24,079, (184) 3.0 179

[0337] TABLE 13 Condition VII in Table 3 Cata- Yield #Me/ m.p. Ex lyst(g) 1000 CH₂ (° C.)(ΔH_(f)) Mw/PDI TON 87 2 6.902 29 121 (145)15,842/5.6 12,302 88 5 13.547 18 122 (167)  8,675/4.6 24,146 89 7 13.85859 106 (110)  3,033/3.3 24,700

[0338] As noted above, one potential problem with the copolymerizationof ethylene (and/or other olefins) and a polar comonomer such as anacrylate is the possibility of obtaining a homopolymer of the polarcomonomer because of free radical polymerization of that polarcomonomer. One method of determining whether such a homopolymer ispresent is to run an NMR spectrum of the polymer(s). Unfortunately,using ¹H-NMR for some of the more common acrylate monomers such asmethyl acrylate the ¹H spectra of the homopolymer and ethylenecopolymers overlap, so a quantitative analysis is difficult. Althoughthis analysis can be done by ¹³C-NMR, it is more difficult, expensiveand time consuming. However, when an acrylate of the formulaH₂C═CHC(O)OR³⁶, wherein R³⁶ is —CH₂CH₂OR³⁷, and R³⁷ is aryl orsubstituted aryl, preferably aryl, is used, the peaks do not overlap atall in the ¹H-NMR spectra, and that is a great advantage in determiningwhether the copolymer is “contaminated” with homopolymer.

[0339] Total methyls per 1000 CH₂ are measured using different NMRresonances in 1H and 13C NMR. Because of accidental overlaps of peaksand different methods of correcting the calculations, the valuesmeasured by ¹H and ¹³C NMR will usually not be exactly the same, butthey will be close, normally within 10-20% at low levels of acrylatecomonomer. In ¹³C NMR the total methyls per 1000 CH2 are the sums of the1B₁, 1B₂, 1B₃, and 1B₄₊, EOC resonances per 1000 CH₂, where the CH₂'s donot include the CH₂'s in the alcohol portions of the ester group. Thetotal methyls measured by 13C NMR do not include the minor amounts ofmethyls from the methyl vinyl ends or the methyls in the alcohol portionof the ester group. By ¹H NMR the total methyls are measured from theintegration of the resonances from 0.6 to 1.08 and the CH₂'s aredetermined from the integral of the region from 1.08 to 2.49 ppm. It isassumed that there is 1 methine for every methyl group, and ⅓ of themethyl integral is subtracted from the methylene integral to remove themethine contribution. The methyl and methylene integrals are alsousually corrected to exclude the values of the methyls and methylenes inthe alcohol portion of the ester group, if this is practical. Because ofthe low levels of incorporation, this is usually a minor correction.

[0340]FIG. 1 shows the ¹H-NMR spectrum of a mixture of an EGPEA (Z=1,R³⁷ is phenyl) homopolymer in a mixture with an EGPEA compolymer withethylene. The spectrum was obtained on a 500 MHz Bruker Avancespectrometer on a 5 mm QNP probe on samples diluted ˜10 mg/0.5 ml intce-d2 at 120° C. using a 90 degree pulse of 14 μsec, a spectral widthof 12.8 kHz, an acquisition time of 2.6 sec and a recycle delay of 30sec. A total of 8 transients were acquired. Spectra were referenced totce-d2 at 5.928 ppm. FIG. 1 also indicates the assignments of thevarious peaks. Using EGPEA (and other acrylates described above)separation of the homopolymer and copolymer peaks is clear andquantitative analysis of the mixture is possible.

[0341] Another NMR analysis used below is end group analysis of ethylenecopolymers with acrylates. 100 MHz ¹³C NMR spectra were obtained on aVarian® Unity 400 MHz spectrometer on typically 10 wt % solutions of thepolymers and 0.05 M CrAcAc in 1,2,4-trichlorobenzene (TCB) in a 10 mmprobe unlocked at 120° C. using a 90 degree pulse of 19.2 Usec, aspectral width of 35 kHz, a relaxation delay of 5 s, an acquisition timeof 0.64 s. and inverse gated decoupling (decoupling only duringacquisition). A few samples were run under similar conditions on aBruker Avance 500 MHz NMR. A typical sample contained 310 mg polymer and60 mg CrAcAc in TCB with a total volume of 3.1 mL (Varian recommendedvolume) in a 10 mm NMR tube; care was taken that the sample was verywell mixed and uniform in consistency. Samples were preheated for atleast 15 min. in the NMR before acquiring data. Data acquisition timewas typically 10.5 hr per sample. The T1 values of the carbons of anethylene/methyl acrylate copolymer sample were measured under theseconditions to be all less than 0.9 s. The longest T1 measured was forthe Bu+, EOC resonance at 14 ppm, which was 0.84 s. Spectra arereferenced to the solvent—the TCB high field resonance at 127.918 ppm.

[0342] Integrals of unique carbons in each branch were measured and werereported as number of branches per 1000 methylenes. Counted in thesemethylenes are those in the backbone (main chain) and branches, but notmethylenes in the alcohol portions of esters, for example the —OCH₂ CH₃methylene in an ethyl ester. These integrals are accurate to ±5%relative for abundant branches and ±10 or 20% relative for branchespresent at less than 10 per 1000 methylenes. FIG. 2 shows such aspectrum together with assignments of various carbon atoms. INDEXFREQUENCY PPM HEIGHT  1 17613.645 175.137   8.7------J  2 16655.651165.612  12.6------W  3 14882.774 147.983  10.5------V  4 13969.102138.898  19.1------F  5 13546.174 134.693  44.9------|  6 13489.570134.130  43.0  |  7 13483.697 134.072  52.0  |  8 13448.453 133.7215119.1  |  9 13401.995 133.260 5131.0 10 13369.955 132.941  93.1 1113359.275 132.835  41.8 12 13319.759 1324.42  16.6 13 13270.631 131.953 36.9 14 13244.999 131.699  75.8 15 13215.095 131.401 5189.6 1613181.453 131.067 4823.7 TCB solvent 17 13154.219 130.796  84.7 1813138.199 130.637  62.3 19 13130.189 130.557  113.2 20 13101.887 130.2765124.1 21 13063.439 129.893  68.1 22 12993.485 129.198   8.3 2312938.484 128.651  43.9 24 12864.792 127.918 4827.4  | 25 12831.684127.589  55.7  | 26 12822.072 127.493  36.1  | 27 12806.586 127.339 25.5------| 28 12504.876 124.339   5.6------A 29 12418.368 123.479  5.7------C 30 12269.383 121.998  12.3------U 31 11479.598 114.145 17.7------E 32 6439.715 64.032  14.7------K 33 6424.764 63.883   9.9 344611.303 45.851   7.9------Y 35 3817.780 37.961   4.1 36 3755.302 37.340 21.6------αB₁ 37 3452.525 34.329  12.7 38 3422.087 34.027   4.3 393395.921 33.767  18.6------αB₂ 40 3322.229 33.034  11.4------MB1 413280.043 32.614  21.7 42 3237.857 32.195  14.6 43 3220.769 32.025 54.8------3B6+,EOC 44 3177.515 31.595  27.6 45 3048.822 30.315  23.2 463037.608 30.204  35.5 47 3000.228 29.832 2905.6------CH2's 48 2968.18829.513  39.1 49 2958.576 29.418  76.7 50 2931.342 29.147  36.8 512926.002 29.094  27.5 52 2856.048 28.398  13.0 53 2777.550 27.618  17.454 2752.986 27.374   6.7 55 2741.238 27.257  24.4------βB2+ 56 2725.75227.103  17.3 57 2599.195 25.844  18.7 58 2286.271 22.733 53.2------2B5+,EOC 59 2271.319 22.584  27.7 60 1993.640 19.823 11.6------1B1 61 1774.166 17.641   4.4 62 1405.173 13.972 52.3------1B4+,EOC 63 1390.755 13.829  30.2 64 1265.799 12.586   5.4

[0343] Details about NMR nomenclature (e.g., 2B₅₊) and other details ofNMR polymer analysis, will be found in previously incorporated U.S. Pat.No. 5,880,241.

[0344] GPC molecular weights are reported versus polystyrene standards.Unless noted otherwise, GPC's were run with RI detection at a flow rateof 1 mL/min at 135° C. with a run time of 30 min. Two columns were used:AT-806MS and WA/P/N 34200. A Waters RI detector was used and the solventwas TCB with 5 grams of BHT per 3.79 L. Dual UV/RI detection GPC as runin THF at rt using a Waters 2690 separation module with a Waters 2410 RIdetector and a Waters 2487 dual absorbance detector. Two Shodex columns,KF-806M, were used along with one guard column, KF-G. In addition toGPC, molecular weight information was at times determined by ¹H NMRspectroscopy (olefin end group analysis) and by melt index measurements(g/10 min at 190° C.).

Example 90 Synthesis of Catalyst 24

[0345] In a drybox, 0.100 g Catalyst 21 and 15 mL toluene were combined.To this orange solution was added 0.177 g tris(pentafluorophenyl)boronat RT. The cloudy orange solution was stirred at RT overnight. Thereaction mixture was filtered through Celite®, followed by 3×5 mLtoluene wash. The filtrate was evaporated to ca. 2 mL and was added 50mL pentane. The yellow precipitate was filtered and washed with 3×5 mLpentane. The product was dried in vacua. Final yield of the yellow solidwas 0.088 g (33%). X-ray single crystal analysis confirmed the proposedstructure (Zwitter-ionic complex). ³¹PNMR in CD₂Cl₂: δ 60.05 (s). ¹HNMRin CD₂Cl₂: (obtained by 1D NOE, 2D ¹H-¹³C correlation (HMQC) and NOESYexperiments): δ 5.42 (sept, central allyl-H, 1H); 4.18 (vd, J=7.9 Hz,syn-terminal allyl-H, on the C═O side, 1H); 3.04 - 3.07 (m, overlappedpeaks of syn-terminal-allyl proton that is close to (t-Bu)₂P andanti-terminal-allyl proton that is close to C═O, 2H total); 2.82 - 2.98(ABX pattern (X is phosphorus), J_(AB)=18.4 Hz, ²J_(PH)=8.3 Hz, PCHH′,2H total); 1.77 (d, ²J_(PH)=12.9 Hz, anti-terminal-allyl-H that is closeto (t-Bu)₂P, 1H); 1.35 (d, ³J_(PH)=14.7 Hz, C(CH₃)₃, 9H); 1.18 (d,³J_(PH)=14.7 Hz, C(CH₃)₃, 9H). ¹⁹FNMR in CD₂Cl₂: δ 134.89 (d, J=20.2 Hz,ortho-F, 6F); −159.75 (t, para-F, 3F); −165.63 (t, meta-F, 6F).

Example 91 Synthesis of Catalyst 25

[0346] In a drybox, 0.3545 g (1.806 mmole) trans-stilbene oxide and 20mL THF were combined. The clear solution was cooled at −30° C. for 0.5h. Then 0.3 g (1.806 mmole) (t-Bu)₂PCH₂Li was added. The resulting paleyellow reaction was stirred at RT for 3 h. The reaction was evaporatedunder full vacuum overnight. ³¹PNMR of the ligand precursor in THF-d₈: δ12.00 (s, major); 26.73 (s, minor) . Then 0.6443 g (1.778 mmole) ligandprecursor and 20 mL THF were combined. To this solution was added 0.2404g (0.889 mmole) nickel allyl chloride dimer. After stirring overnight,the reaction was evaporated under full vacuum. To the resulting residuewas added 20 mL toluene. The solution was filtered through Celite®,followed by 3×10 mL toluene wash. The filtrate was evaporated under fullvacuum. To the residue was added 30 mL pentane and the resulting solidwas stirred for several minutes. The solid was filtered and was washedwith 3×10 mL pentane. The sample was dried in vacuo for several hours.Final weight of the light brown solid was 51.4 mg (6%).

Example 92 Synthesis of Catalyst 26

[0347] In a drybox, 0.387 g (1.972 mmole) trans-stilbene oxide and 20 mLTHF were combined. The clear solution was cooled to −30° C. for 0.5 h.Then 0.3 g (1.972 mmole) (t-Bu)₂PLi was added. The amber reaction wasstirred at RT for 2.5 h. The reaction was then evaporated under fullvacuum. Then 0.6769 g (1.943 mmole) ligand precursor and 20 mL THF werecombined. To the reaction was added 0.2627 g (0.9715 mmole) nickel allylchloride dimer. After stirring overnight, the reaction was evaporatedunder full vacuum. To the resulting residue was added 20 mL toluene. Thesolution was filtered through Celite®, followed by 3×10 mL toluene wash.The filtrate was evaporated under full vacuum to dryness. Final weightof the dark brown solid was 0.5148 g (60%).

Example 93 Synthesis of Catalyst 27

[0348] In a drybox, 0.300 g (1.806 mmole) (t-Bu)₂PCH₂Li and 20 mL THFwere combined in a 50 mL Schlenk flask. The flask was removed from thedrybox, placed on the Schlenk line, and degassed. After cooling the paleyellow solution to 0° C. with an ice bath, SO₂ was applied at 1 atm. Theice bath was removed after 20 min and the reaction was allowed to warmto RT. After 15 min, SO₂ was discontinued. The reaction mixture wasstirred for an additional 25 min. The reaction mixture was thenevaporated to remove excess SO₂. The reaction mixture was transferredinto a drybox. The solution was evaporated under full vacuum overnight.Then 0.4058 g (1.763 mmole) ligand precursor and 20 mL THF werecombined. To this yellow solution was added 0.2385 g (0.882 mmole)nickel allyl chloride dimer. The dark red reaction mixture was stirredat RT for 2 h. The reaction mixture was then evaporated under fullvacuum. The resulting red residue was triturated with 25 mL pentane. Thesolid was filtered and washed with 3×10 mL pentane. The sample was driedin vacuo for 45 minutes.

Example 94 Synthesis of Catalyst 28

[0349] In a drybox, 0.6214 g (3.01 mmole) bis(trimethylsilyl)sulfurdiimide and 20 mL THF were combined. The yellow solution was cooled at−30° C. for 45 min. Then 0.5 g (3.01 mmole) (t-Bu)₂PCH₂Li was added. Theorange-brown reaction mixture was stirred at RT for 1 h. To the reactionmixture was added 0.407 g (1.505 mmole) nickel allyl chloride dimer. Thered solution was stirred at RT for 3 h. The reaction mixture was thenevaporated under full vacuum overnight. To the residue was added 20 mLtoluene. The solution was filtered through Celite®, followed by 3×10 mLtoluene wash. The filtrate was evaporated under full vacuum. Finalweight of the orange-brown solid was 1.0114 g (72%) . ³¹PNMR in THF-d₈:δ 93.78 (s)

Example 95 Synthesis of Catalyst 29

[0350] In a drybox, 0.4189 g (3.01 mmole) N-thionylaniline and 20 mL THFwere combined. The clear solution was cooled at −30° C. for 0.5 h. Then0.5 g (3.01 mmole) (t-Bu)₂PCH₂Li was added. The resulting orange-brownreaction was stirred at RT for 1 h. To the reaction mixture was added0.407 g (1.505 mmole) nickel allyl chloride dimer. The red solution wasstirred for 3 h at RT. The reaction mixture was then evaporated underfull vacuum. To the residue was added 5 mL toluene, followed by 50 mLpentane. The resulting solid was stirred for several min, filtered, andwashed with 3×10 mL pentane. Final weight of the dull orange-yellowsolid was 0.884 g (67%). ³¹PNMR in THF-d₈: 77.18 (s)

Example 96 Synthesis of Catalyst 30

[0351] In a drybox, 0.485 g (3.01 mmole) 1-methylisatin and 20 mL THFwere combined. The orange solution was cooled at −30° C. for 45 min.Then 0.500 g (3.01 mmole) (t-Bu)₂PCH₂Li was added. The reaction mixtureturned purple and it was stirred at RT for 1 h. To the reaction mixturewas added 0.407 g (1.505 mmole) nickel allyl chloride dimer. The redsolution was stirred at RT for 3 h. The reaction mixture was thenevaporated under full vacuum overnight. To the residue was added 20 mLtoluene. The solution was filtered through Celiteo, followed by 3×10 mLtoluene wash. The filtrate was evaporated under full vacuum. Finalweight of the dark brown solid was 1.463 g.

Example 97 Synthesis of Catalyst 31

[0352] In a drybox, 0.6646 g (1.765 mmole) ArN═C(H)—C(H)═NAr(Ar=2,6-diisopropylphenyl) and 20 mL THF were combined. The yellowsolution was cooled at −30° C. for 0.5 h. Then 0.2932 g (1.765 mmole)(t-Bu)₂PCH₂Li was added. The resulting orange-red reaction was stirredat RT for 1 h. To the reaction was added 0.2386 g (0.8825 mmole) nickelallyl chloride dimer. The red solution was stirred at RT for 3 h. Thereaction was then evaporated under full vacuum. To the residue mixturewas added 20 mL toluene. The solution was filtered through Celite®,followed by 3×10 mL toluene wash. The filtrate was evaporated under fullvacuum. Final weight of the dark brown solid was 0.6937 g (62%).

Example 98 Synthesis Catalyst 32

[0353] In a drybox, 0.250 g (1.64 mmole) sodium chloromethylsulfonateand 20 mL THF were combined. The mixture was cooled to −30° C. for 0.5h. Then 0.25 g (1.64 mmole) (t-Bu)₂PLi was added and the mixture wasstirred and allowed to slowly warm up to RT. As it warmed, the reactionmixture became cloudy orange. The reaction mixture was stirred at RT fortwo days. The resulting cloudy brown solution was evaporated under fullvacuum. Then 0.425 g (1.62 mmole) ligand precursor and 20 mL THF werecombined. To this brown suspension was added 0.219 g (0.81 mmole) nickelallyl chloride dimer. The resulting red-brown reaction mixture wasstirred at RT for 3 h. The reaction mixture was then evaporated underfull vacuum to dryness. The sample was triturated with 25 mL pentane.The solid was filtered and washed with 3×10 mL pentane. It was dried invacuo for 1.5 h. Final weight of the light brown solid was 0.369 g(67%).

Example 99 Synthesis of Catalyst 33

[0354] In a dry box, to a 100 mL flask containing 10 mL of THF solutionof 1,3-diisopropylcarbodiimide (0.0816 g, 0.64 mmole), was slowly addedthe THF solution of (t-Bu)₂PCH₂Li (0.107 g, 0.64 mmole). The solutionchanged from yellow to colorless upon stirring overnight. Solvent wasremoved. The residue was rinsed with pentane. White powder (0.136 g,0.467 mmole) was obtained in 72% yield. ¹H NMR of the ligand precursor(in C₆D₆) : δ 0.98 (d, 18H, t-Bu-H); 1.3 (dd, 12H, —CH (CH₃)₂) ; 1.96(s, d, 2H, PCH₂) ; 3.80 (m, 2H, —CH(CH₃)₂) . It contained one equivalentof hydrolyzed product that might be resulted of hydrolysis of thelithium salt during the period outside of the drybox. ³¹PNMR (C₆D₆) : δ21.837 (s); 13.177 (s). In the dry box, 0.0542 g (0.185 mmole) of theligand precursor and 0.0441 g (0.092 mmole) allyl-Ni-bromide dimer{((2-MeO₂C—C₃H₄)NiBr)₂} were mixed in 10 mL THF in a 50 mL flask. Themixture was stirred for 1 h. THF was removed in vacuo and the residuewas extracted with ether. After removal of ether, the product was washedwith pentane. Light brown solid (0.0434 g, 0.098 mmole) was obtained in53% yield. ³¹PNMR (C₆D₆): δ 61.89 (s).

Example 100 Synthesis of Catalyst 34

[0355] In a dry box, to a 100 mL RB flask containing 10 mL THF solutionof 1,3-bis-(2,6-diisopropylphenyl) carbodiimide (0.245 g, 0.675 mmole),was slowly added THF solution of (t-Bu)₂PCH₂Li (0.112 g, 0.675 mmole).Upon stirring overnight, the solution turned from yellow to colorless.Solvent was removed and the product was washed with pentane. Whitepowder (0.272 g, 0.514 mmole) was obtained in 76% yield. ¹HNMR (C₆D₆): δ0.98 (d, 24H, —CH(CH₃)₂) ; 1.37 (d, 18H, t-Bu-H) 2.41 (d, 2H, PCH₂);3.26 (m, 2H, —CH(CH₃)₂); 3.56 (m, 2H, —CH(CH₃)₂); 6.92 - 7.60 (m, 6H,Ar—H). ³¹PNMR (C₆D₆): δ 19.12 (s). In the dry box, 0.0814 g (0.154mmole) of the ligand precursor and 0.0366 g (0.077 mmole) of theallyl-Ni-bromide dimer (((2-MeO₂C—C₃H₄)NiBr)₂) were mixed in 10 mL THFin a 50 ml RB flask and the mixture was stirred for 1 h. THF was removedin vacuo and the residue was extracted with ether. Upon removal of theether, the product was washed with pentane. Yellow powder (0.0906 g,0.133 mmole) was obtained in 87% yield. ³¹PNMR (C₆D₆): δ 59.68 (s).

Example 101 Synthesis of Catalyst 35

[0356] In a dry box, to the 100 mL RB flask containing 10 mL of THFsolution of 1,3-bis(trimethylsilyl) carbodiimide (0.0813 g, 0.436mmole), was added slowly a THF solution of (t-Bu)₂PCH₂Li (0.0725 g,0.436 mmole). The solution turned from yellow to colorless afterstirring overnight. Solvent was removed. The white solid residue, whichis soluble in pentane, was mixed with 0.1036 g (0.218 mmole) ofallyl-Ni-bromide complex (((2-MeO₂C—C₃H₄)NiBr)₂) in 30 mL THF. Themixture was stirred for an hour. Solvent was then removed under vacuum.The residue was extracted with ether. Solvent was removed. The solid wasrinsed with pentane. Orange powder (0.0515 g, 0.102 mmole) was obtainedin 23% yield. ¹HNMR (C₆D₆) : δ 0.21 (s, 1H, allyl-H) ; 0.25 (s, 18H, —Si(CH₃)₃ ) ; 0.94 (d, 19H, t-Bu-H and allyl-H) ; 1.28 (s, 2H, PCH₂) ; 3.0(s, 1H, allyl-H) ; 3.3 (s, 3H, —OCH₃); 3.62 (s, 1H, allyl-H). ³¹PNMR(C₆D₆): δ 57.65.

Example 102 Synthesis of Catalyst 36

[0357] In a dry box, to a 100 mL RB flask containing 10 mL of THFsolution of 1,3-dicyclohexylcarbodiimide (0.143 g, 0.694 mmole), wasadded slowly a THF solution of (t-Bu)₂PCH₂Li (0.115 g, 0.694 mmole) atRT. The color of the solution turned yellow and the mixture was stirredovernight. Solvent was removed under vacuum and the white solid residuewas mixed with 0.1649 g (0.348 mmole) of allyl-Ni-bromide complex(((2-MeO₂C—C₃H₄)NiBr)₂) in 30 mL of THF. The mixture was stirred for 1h. Solvent was then removed under vacuum. The residue was extracted withether. Ether was then removed. The solid was rinsed with pentane. Orangepowder (0.150 g, 0.287 mmole) was obtained in 41% yield. ³¹PNMR (C₆D₆):δ 62.55 (s).

Example 103 Synthesis of Catalyst 37

[0358] In a dry box, to a 100 mL RB flask containing 10 mL THF solutionof 1-naphthylisothiocyanate (0.079 g, 0.426 mmole), was slowly added aTHF solution of (t-Bu)₂PCH₂Li (0.0709 g, 0.426 mmole) at −30° C. Thesolution turned yellow orange and it was stirred for one h while thesolution warmed up to RT. Solvent was removed. The solid residue wasmixed with 0.101 g (0.312 mmole) of allyl-Ni-bromide complex(((2-MeO₂C—C₃H₄)NiBr)₂) in 30 mL THF. The mixture was stirred for 1 h.Solvent was removed under vacuum. The residue was extracted with ether.Solvent was evaporated and the product was rinsed with pentane. Brownpowder (0.176 g, 0.351 mmole) was obtained in 82% yield. ³¹PNMR (C₆D₆):δ 73.43 (s, major)

Example 104 Synthesis of Catalyst 38

[0359] In a dry box, to a 100 mL RB flask containing 10 mL THF solutionof cyclohexylisothiocyanate (0.0439 g, 0.311 mmole), was added slowly aTHF solution of (t-Bu)₂PCH₂Li (0.0568 g, 0.311 mmole) at −30° C. Thesolution turned yellow orange it was stirred for 1 h, during which timethe solution warmed up to RT. Solvent was removed. The solid residue wasmixed with 0.0739 g (0.156 mmole) of allyl-Ni-bromide complex(((2-MeO₂C—C₃H₄)NiBr)₂) in 30 mL THF. The mixture was stirred for 1 h.Solvent was removed under vacuum. The residue was extracted with ether.The solvent was removed. The product was rinsed with pentane. Brownpowder (0.0773 g, 0.169 mmole) was obtained in 54% yield. ³¹PNMR (C₆D₆):δ 66.69 (s, major).

Example 105 Synthesis of Catalyst 39

[0360] In a dry box, benzoylisocyanate (0.1966 g, 1.336 mmole) wasdissolved in 20 mL THF in a 100 mL RB flask. The solution was cooled toca. −30° C. in a freezer. (t-Bu)₂PCH₂Li (0.2220 g, 1.336 mmole) wasadded to the above cold solution under stirring. The mixture turned darkred. It was allowed to stir at RT for 4 h. The solution was thenevaporated to dryness. To the ligand precursor (ca. 1.300 mmole) wasadded 20 mL THF. Under stirring, nickel allyl chloride dimer 0.1760 g,0.6500 mmole) was added to the mixture. The solution became dark red. Itwas allowed to stir at RT for 2 h. Solvent was evaporated. Toluene (ca.8 mL) was added to the brick red residue. Upon brief stirring, largeexcess of pentane was added. The resulting solid was filtered, followedby 3× pentane wash, and dried in vacuo. Pale orange solid (0.4223 g,72%) was obtained.

Examples 106-120

[0361] Polymerizations with catalysts 24 through 38 are shown in Tables14 and 15. TABLE 14 Condition I in Table 3 #Me/ Cata- Yield 1000 m.p. Exlyst (g) CH₂ (° C.)(ΔH_(f)) Mw/PDI TON 106  24* 7.81 26 118 (52.2) 4,495/4.9 13,900 107 25 2.89 15 123 (0.6)  17,614/8.9 5,150 108 26 8.2621 122 (173.1)  19,394/11.21 4,700 109 27 4.66 33 129 (147.6)226,688/8.8 8,300 110 28 1.07 20 127 (182.2)  34,420/33.5 1,900 111 296.14 17 123 (159.3)  12,964/5.2 10,900 112 30 9.71 32 123 (172.2) 4,898/8.1 17,300 113 31 7.82 13 121 (126.8) 563,495/5.1 13,900 114 3211.75 12 131 (225.5) 254,365/106.4 20,940

[0362] TABLE 15 Ethylene Polymerization Using 0.02 mmole Catalyst, 5 mLTCB and 10 eq B(C₆F₅)₃, at RT under 6.9 MPa Ethylene for 18 h Yield #Me/m.p. (° C.) Ex Catalyst (g) 1000 CH₂ (ΔH_(f)) Mw TON 115 33 4.427 27 129Trimodal 7604 (173.8) 116 34 0.181 25 117 Trimodal  343 (116.9) 117 350.698 15 126 67,352 1160 (190.1) 118 36 3.388 27 128 Insoluble 4452(165.6) in TCB 119 37 0.083 35 130 Trimodal  140 (137.2) 120 38 0.321 21129 70,329  535 (168.5)

Examples 121-150

[0363] Examples 121-150 are listed in Tables 16-20 below. The structuresfor these compounds illustrate just one of the possible products andbinding modes that may have formed during the synthesis of the ligandand the subsequent synthesis of the nickel compound and are not meant tobe restrictive. The polymerizations were carried out according toGeneral Polymerization Procedure A. Varying amounts of acrylatehomopolymer are present in some of the samples. In Tables 16-20, theyield of the polymer is reported in grams and includes the yield of thedominant ethylene/acrylate copolymer as well as the yield of anyacrylate homopolymer that was formed. Molecular weights were determinedby GPC, unless indicated otherwise. All copolymerizations were run for18 h, unless otherwise noted.

[0364] General Polymerization Procedure A: In a drybox, a glass insertwas loaded with the nickel compound and, optionally, a Lewis acid (e.g.,BPh₃ or B(C₆F₅)₃) and borate (e.g., NaBAF or LiBArF) and any otherspecified cocatalysts. Next, the solvent was added to the glass insertfollowed by the addition of any co-solvents and then comonomers. Theinsert was greased and capped. The glass insert was then loaded in apressure tube inside the drybox. The pressure tube was then sealed,brought outside of the drybox, connected to the pressure reactor, placedunder the desired ethylene pressure and shaken mechanically. After thestated reaction time, the ethylene pressure was released and the glassinsert was removed from the pressure tube. The polymer was precipitatedby the addition of MeOH (˜20 mL). The polymer was then collected on afrit and rinsed with MeOH and, optionally, acetone. The polymer wastransferred to a pre-weighed vial and dried under vacuum overnight. Thepolymer yield and characterization were then obtained. TABLE 16 EthyleneHomopolymerizations, (0.02 mmol Cmpd, 25° C., 1.0 MPa, 10 mL TCB, 10equiv B(C₆F₅)₃) NaBAF PE PE Total Ex. Cmpd equiv g TO M.W. Me 121 40 10 1.08^(a) 1,920 M_(w) = 37,044; M_(n) = 4,989; M_(w)/M_(n) = 7.43 22.4122 40 1 2.49^(a) 4,440 M_(w) = 34,072; M_(n) = 4,693; M_(w)/M_(n) =7.26 44.6 123 42 0 1.01 1,800 M_(w) = 25,754; M_(n) = 905 M_(w)/M_(n) =28.46 79.2 124 43 0 1.79 3,190 M_(w) = 12,361; M_(n) = 519; M_(w)/M_(n)= 23.80 59.4

[0365] TABLE 17 Ethylene/Acrylate Copolymerizations (6.9 MPa, 100° C.)(0.02 mmol Cmpd, 10 mL total of TCB + Acrylate, 20 equiv B(C₆F₅)₃)Acrylate Acrylate NaBAF Incorp. Total Ex. Cmpd mL equiv Yield g mol %M.W. Me 125 42 EGPEA 1 0 0.38 0.5 M_(w)(¹H) = 3,531 19.7 126 41 EGPEA 10 0.077 0.3 M_(n)(¹H) = 16,192 17.7 127 43 EGPEA 1 0 0 128 44 EGPEA 1 00.094 0.4 M_(w) = 3,259; M_(p) = 1,067; nd M_(n) = 988; M_(w)/M_(n) =3.30 129 40 EGPEA 1 0 0.10 1.3^(a) M_(w) = 11,396; M_(p) = 7,282; 6.9M_(n) = 4,581; M_(w)/M_(n) = 2.49 130 40 EGPEA 1 1 2.40 0.66 ¹³C M_(w) =6,649; M_(p) = 6,271 nd 0.33 IC M_(n) = 3,104; M_(w)/M_(n) = 2.14 0.33EG 131 40 EGPEA 1 20 8.61 0.38 ¹³C M_(w) = 6,674; M_(p) = 5,860; nd 0.19IC M_(n) = 3,209; M_(w)/M_(n) = 2.08 0.19 EG 132 40 EGPEA 2 20 5.50 0.77¹³C M_(n) = 5,238; M_(p) = 4,484; nd 0.39 IC M_(n) = 2,423; M_(w)/M_(n)= 2.16 0.38 EG 133 41 EGPEA 2 20 0.61 A M_(w) = 5,032; M_(p) = 4,711; ndM_(n) = 2,330; M_(w)/M_(n) = 2.16 134 42 EGPEA 2 20 1.06 1.0 M_(w) =4,237; M_(p) = 3,286; 14.2 M_(n) = 1,548; M_(w)/M_(n) = 2.74 135 43EGPEA 2 20 0.70 A nd nd 136 40 EGPEA 4 20 2.02 0.70 M_(w) = 3,201; M_(p)= 2,755; 11.0 M_(n) = 1,688; M_(w)/M_(n) = 1.90 137 40 MA 0.5 10 13.210.41 ¹³C M_(w) = 5,008; M_(p) = 4,932; 8.6 0.21 IC M_(n) = 1,582;M_(w)/M_(n) = 3.16 0.20 EG 138 40 MA 0.5 20 11.45 0.57 ¹³C M_(w) =4,461; M_(p) = 3,994; 10.2 0.33 IC M_(n) = 1,755; M_(w)/M_(n) = 2.540.24 EG 139 40 HA 2 20 1.48 0.60 ¹³C M_(w) = 4,034; M_(p) = 3,699; 7.40.21 IC M_(n) = 1,849; M_(w)/M_(n) = 2.18 0.39 EG 140 40 HA 1 20 9.880.36 ¹³C M_(w) = 5,834; M_(p) = 5,525; 8.2 0.15 IC M_(n) = 2,251;M_(w)/M_(n) = 2.59 0.21 EG 141 40 EGPEA 1 10 0.40 0.5 M_(w) = 7,123;M_(n) = 3,183; 8.5 .005 mmol M_(p) = 6,843; M_(w)/M_(n) = 2.24

[0366] TABLE 18 Ethylene/Acrylate Copolymerizatioris (6.9 MPa) (0.02mmol Cmpd, 18 h, 10 mL total of TCB + EGPEA, 20 equiv B(C₆F₅)₃, 10 equivNaBAF) Acrylate EGPEA Temp. Incorp. Total Ex. Cmpd mL ° C. Yield g mol %M.W. Me 142 40 2 120 12.40 0.69 ¹³C M_(w) = 3,813; M_(n) = 1,577; nd0.37 IC M_(n) = 3,234; M_(w)/M_(n) = 2.42 0.32 EG 143 40 4 120 5.16Trace^(a) M_(w) = 2,660; M_(p) = 2,528; nd M_(n) = 1,305; M_(n)/M_(n) =2.04 144 41 2 120 5.30 1.1 M_(w) = 3,331; M_(p) = 3,047; 13.8 M_(n) =1,386; M_(w)/M_(n) = 2.40 145 40 4 120 3.30 1.5 M_(w) = 3,125; M_(p) =3,139; 16.8 M_(n) = 1,476; M_(w)/M_(n) = 2.12 146 40 4 120 4.10 2.2 14740 2 130 8.99 2.8 M_(w) = 3,479; M_(p) = 3,202; 25.7 M_(n) = 1,510;M_(w)/M_(n) = 2.30 148 40 2 120 4.57 2.2 M_(w) = 3,914; M_(p) = 3,592;32 0.001 mol M_(n) = 1,761; M_(w)/M_(n) = 2.22

[0367] TABLE 19 Ethylene/Acrylate Copolymerizations (3.5 MPa, 120° C.)(18 h, 10 mL total of TCB + EGPEA, 20 equiv B(C₆F₅)₃, 10 equiv NaBAF)Acrylate EGPEA Temp. Yield Incorp. Total Ex. Cmpd mL ° C. G mol % M.W.Me 149 40 1 120 2.48 0.69 ¹³C M₂ = 3,675; M_(p) = 3.403; nd  0.01 mmol0.37 IC M_(n) = 1,701; M_(w)/M_(n) = 2.16 0.32 EG 150 40 1 120 0.21Trace^(a) M_(w) = 3,272; M_(p) = 3,403; nd 0.005 mmol M_(n) = 1,701;M_(n)/M_(w) = 2.01

[0368] TABLE 20 Branching Analysis for Some MA and HA Copolymers ofTable 17^(a) Ex. Total Me Me Et Hex+ & eoc Am+ & eoc Bu+ & eoc Me ester137 8.6 2.4 1.0 6.4 5.8 5.2 2.5 138 10.2  2.5 2.1 7.5 6.1 5.6 3.9 1397.4 2.4 0.6 5.3 5.0 140 8.2 3.1 5.1 5.1

Examples 151-439

[0369] Examples 151-439 are listed in Tables 21-57 below. They werecarried out with nickel complexes 45-97 shown above. For each of 45-97the counterion is BAF. The polymerizations were carried out according toGeneral Polymerization Procedure A. Varying amounts of acrylatehomopolymer are present in some of the isolated polymers. In Tables21-58, the yield of the polymer is reported in grams and includes theyield of the dominant ethylene/acrylate copolymer as well as the yieldof any acrylate homopolymer that was formed. Molecular weights weredetermined by GPC, unless indicated otherwise. Mole percent acrylateincorporation and total Me were determined by ¹H NMR spectroscopy,unless indicated otherwise. Mole percent acrylate incorporation istypically predominantly IC, unless indicated otherwise. The LiB(C₆F₅)₄used (LiBArF) included 2.5 equiv of Et₂O. All copolymerizations were runfor 18 h, unless otherwise noted. TABLE 21 Reproducibility ofEthylene/Acrylate Copolymerizations Using 45 (0.02 mmol Cmpd, 6.9 MPa.,120° C., 18 h, 10 mL Total of TCB + Acrylate, 40 eguiv B(C₆F₅)₃)Acrylate Acrylate Yield Incorp. Total Ex. mL g mol % M.W. Me 151 EGPEA9.77 1.20 (¹³ C) M_(p) = 8,651; M_(w) = 8,930; M_(n) = 3,983; PDI = 2.2454.6 2 152 EGPEA 12.47 1.4 M_(p) = 12,036; M_(w) = 12,662; M_(n) =4,449; PDI = 2.85 51.8 2 153 EGPEA 10.73 2.0 M_(p) = 13,657; M_(w) =14,740; M_(n) = 5,348; PDI = 2.76 54.5 2 154 HA 2.08 1.28 (¹³ C) M_(p) =6,838; M_(w) = 6,534; M_(n) = 1,331; PDI = 4.91 53.2 2 155 HA 2.42 1.16(¹³ C) M_(p) = 6,625; M_(w) = 7,524; M_(n) = 3,305; PDI = 2.28 54.9 2

[0370] TABLE 22 Variation of Acrylate Concentration, Acrylate Structure,Solvent and Temperature in Ethylene/Acrylate Copolymeriza- tions Using45 (0.02 mmol Cmpd, 6.9 MPa E, 18 h, 10 mL Total of TCB + Acrylate, 40equiv B(C₆F₅)₃) Acrylate Temp Yield Acryl. Incorp. Total Ex. mL ° C. g(mol %) M.W. Me 156 EGPEA 120 16.72 0.7 M_(p) = 12,452; M_(w) = 13,952;69.8 1 M_(n) = 4,319; PDI = 3.23 157 EGPEA 120 12.47 1.4 M_(p) = 12,036;M_(w) = 12,662; 51.8 2 M_(n) = 4,449; PDI = 2.85 158 EGPEA 120 5.37 2.70(¹³C) M_(p) = 6,623; M_(w) = 9,878; 42.6 4 M_(n) = 3,388; PDI = 2.92(¹³C) 159 EGPEA 100 4.21 1.60 (¹³C) M_(p) = 20,949; M_(w) = 21,275; 26.12 M_(n) = 9,605; PDI = 2.21 (¹³C) 160 EGPEA 100 3.13 3.60 (¹³C) M_(p) =12,760; M_(w) = 14,733; 20.6 4 M_(n) = 6,092; PDI = 2.42 (¹³C) 161IDA^(a)  80 0.89  1.6 (¹³C) nd nd 2 162 IDA^(b)  80 1.75 nd M_(p) =30,258; M_(w) = 32,201; nd 1 M_(n) = 13,047; PDI = 2.47 163 HA 120 2.700.66 (¹³C) M_(p) = 8,851; M_(w) = 9,678; 54.7 1 M_(n) = 2,252; PDI =4.30 164 HA 120 2.08 1.28 (¹³C) M_(p) = 6,838; M_(w) = 6,534; 53.2 2M_(n) = 1,331; PDI = 4.91 165 MA 120 13.08 0.10 (¹³C)^(c) M_(p) =10,797; M_(w) = 12,929; 76.0 0.25 M_(n) = 4,798; PDI = 2.69 166 MA 12013.17 0.17 (¹³C)^(d) M_(p) = 12,267; M_(w) = 13,485; 72.0 0.5 M_(n) =4,587; PDI = 2.94 167 MA 120 15.45 0.19 (¹³C)^(d) M_(p) = 13,376; M_(w)= 13,971; 78.6 1 M_(n) = 4,694; PDI = 2.98

[0371] TABLE 23 Variation of Acrylate Concentration and Temperature inEthylene/EGPEA Copolymerizations with Cmpd. 46 (0.02 mmol Cmpd, 6.9 MPaE, 18 h, 10 mL Total of TCB + EGPEA, 40 equiv B(C₆F₅)₃) Acrylate EGPEATemp Incorp. Total Ex. mL ° C. Yield g mol % M.W. Me 168 2 120 2.17 0.03(¹³C) M_(p) = 12,550; M_(w) = 13,744; M_(n) = 5,936; PDI = 2.32 169 2100 1.88 0.44 (¹³C) M_(p) = 17,362; M_(w) = 17,905; 28.6 M_(n) = 8,075;PDI = 2.16 170 4 120 1.22 Nd^(a) M_(p) = 8,651; M_(w) = 8,930; M_(n) =3,983; PDI = 2.24 171 4 100 0.032 1.1 M_(p) = 13,111; M_(w) = 13,076;24.3 M_(n) = 6,062; PDI = 2.16

[0372] TABLE 24 Effect of Counterion on Ethylene/EGPEA CopolymerizationsUsing Cmpd 45 (0.02 mmol Cmpd, 6.9 MPa E, 120° C., 18 h, 8 mL TCB, 2 mLEGPEA, 40 equiv B(C₆F₅)₃) Acrylate Incorp. Total Ex. Counterion Yield gmol % M.W. Me 172 [B[3,5-C₆H₃—(CF₃)₂]₄]⁻ 12.47 1.4 M_(p) = 12,036; M_(w)= 12,662; 51.8 M_(n) = 4,449; PDI = 2.85 173 [B(C₆F₅)₄]⁻ 16.72 1.5 M_(p)= 15,316; M_(w) = 17,100; 57.1 M_(n) = 6,108; PDI = 2.80 174[N(SO₂CF₃)₂]⁻ 5.38 1.9 M_(p) = 12,551; M_(w) = 13,097; 52.6 M_(n) =4,949; PDI = 1.78

[0373] TABLE 25 Effect of Bu₂O Addition on Ethylene/AcrylateCopolymeriza- tions Using Cmpd 45 (0.02 mmol Cmpd, 6.9 MPa E, 120° C.,18 h, 8 mL Total of TCB + Bu₂O, 2 mL EGPEA, 40 equiv B(C₆F₅)₃) BU₂O^(a)Acrylate Total Ex. mL Yield g Incorp. mol % M.W. Me 175 0 12.47 1.4M_(p) = 12,036; M_(w) = 12,662; 51.8 M_(n) = 4,449; PDI = 2.85 176 25.10 1.72 (¹³C) M_(p) = 6,952; M_(w) = 8,846; 65.0 M_(n) = 3,044; PDI =2.91 177 4 8.73 1.08 (¹³C) M_(p) = 7,135; M_(w) = 8,894; 66.5 M_(n) =3,313; PDI = 2.68 178 8 11.94 b Dual UV/RI. Nd UV: M_(p) = 7,616; M_(w)= 50,244; M_(n) = 1,819; PDI = 27.62; RI: M_(p) = 12,075; M_(w) =14,395; M_(n) = 5,150; PDI = 2.80

[0374] TABLE 26 Variation of the Lewis Acid (LA) Cocatalyst inEthylene/Acrylate Copolymerizations, Including Copolymerization in theAbsence of a Lewis Acid Cocatalyst (0.02 mmol Cmpd, 6.9 MPa E; 120° C.,18 h, 10 mL Total of TCB + Acrylate) Acrylate Acrylate Yield Incorp.Total Ex. Cmpd mL LA/equiv g Mol % M.W. Me 179 45 EGPEA B(C₆F₅)₃ 12.471.4 M_(p) = 12,036; M_(w) = 12,662, 51.8 2 40 M_(n) = 4,449; PDI = 2.85180 45 EGPEA BPh₃ 2.73 2.2 M_(p) = 11,442; M_(w) = 13,348; 49.5 2 40M_(n) = 4,897; PDI = 2.73 181 45 EGPEA AlPh₃ 1.15 a M_(p) = 3,207; M₂ =4,233; Nd 2 40 M_(n) = 1,723; PDI = 2.46 182 45 EGPEA B(C₆F₅)₃ 16.72 0.7M_(p) = 12,452; M_(w) = 13,952; 69.8 1 40 M_(n) = 4,319; PDI = 3.23 18345 EGPEA B(C₆F₅)₃ 2.62 0.23 (¹³C) M_(p) = 12, 529; M_(w) = 12,302; 55.81 5 M_(n) = 5,147; PDI = 2.39 184 46 THA B(C₆F₅)₃ 2.37  0.23 M_(p) =12,775; M₂ = 13,777; 2 40 M_(n) = 7,165; PDI = 1.92 185 46 THA None 0.630.64 (¹³C) Dual UV/RI. 34.0 2 UV: M_(p) = 8,098; M₂ = 687,552, M_(n) =6,306; PDI = 109.04; RI: M_(p) = 9,383 ; M_(w) = 12,732; M_(n) = 5,694;PDI = 2.24

[0375] TABLE 27 Effect of alpha-Diimine Structure on Ethylene/AcrylateCopolymerizations (0.02 mmol Cmpd, 6.9 MPa E, 120° C., 18 h, 9 mL TCB, 1mL EGPEA, 40 equiv B(C₆F₅)₃) Acrylate Incorp. Total Ex. Cmpd Yield g mol% M.W. Me 186 45 16.72 0.7 M_(p) = 12,452; M_(w) = 13,952; 69.8 M_(n) =4,319; PDI = 3.23 187 47 14.02 0.8 M_(p) = 9,915; M_(w) = 13,027; 69.5M_(n) = 3,660; PDI = 3.56 188 48 0 — — — 189 50 3.96 0.55 (¹³C) M_(p) =14,350; M_(w) = 15,584; 72.0 (¹³C) M_(n) = 7,421 190 51 2.28 1.8 M_(p) =15,543; M_(w) = 17,651; 64.8 M_(n) = 7,561; PDI = 2.33 191 55 7.64 1.6M_(p) = 14,350; M_(w) = 15,584; 68.6 M_(n) = 7,421 192 56 8.81 Nd^(c)M_(p) = 946; M_(w) = 7,044; Nd M_(n) = 911; PDI = 7.73 193 57 12.28 1.1M_(p) = 14,408; M_(w) = 16,770; 71.7 M_(n) = 6,740; PDI = 2.49 194 5818.19 1.0 M_(p) = 14,315; M_(w) = 15,940; 85.6 M_(n) = 5,887; PDI = 2.71195 59 15.30 0.8 M_(p) = 12,221; M_(w) = 16,421; 78.6 M_(n) = 5,647; PDI= 2.91 196 60 0 — — — 197 61 16.78 0.8 M_(p) = 13,852; M_(w) = 16,074;77.0 M_(n) = 4,701; PDI = 3.42 198 62 2.28 0.9 M_(p) = 1,162; M_(w) =1,609; 75.2 M_(n) = 642; PDI = 2.51 199 63 1.08 1.6 M_(p) = 10,915;M_(w) = 12,370; 74.2 M_(n) = 5,370; PDI = 2.30 200 64 5.32 1.6 M_(p) =42,905; M_(w) = 43,993; 105.0 M_(n) = 16,290; PDI = 2.70 201^(a) 64 5.550.3 RI (THF, rt): M_(p) = 101,394; 101.5 M_(w) = 1,154,459; M_(n) =5,516; PDI = 209.31 202^(a) 64 1.66^(b) 0.3 RI (THF, rt): M_(p) =94,326; 99.5 M_(w) = 5,952,749; M_(n) = 8,304; PDI = 716.88

[0376] TABLE 28 Effect of alpha-Diimine Structure on Ethylene/AcrylateCopolymerizations (0.02 mmol Cmpd, 6.9 MPa E; 120° C., 18 h, 8 mL TCB, 2mL of EGPEA, 40 equiv B(C₆F₅)₃) Acrylate Incorp. Total Ex. Cmpd Yield gmol % M.W. Me 203 45 12.47 1.4 M_(p) = 12,036; M_(w) = 12,662; 51.8M_(n) = 4,449; PDI = 2.85 204 46 2.17 0.03 (¹³C) M_(p) = 12,550; M_(w) =13,744; M_(n) = 5,936; PDI = 2.32 205 47 4.10 2.0 M_(p) = 8,181; M_(w) =9,903; 59.9 M_(n) = 3,243; PDI = 3.05 206 48 0 — — — 207 49 0 — — — 20850 1.10 1.7 Dual UV/RI. 60.5 UV: M_(p) = 19,292; M_(w) = 374,248; M_(n)= 7,268; PDI = 51.49; RI: M_(p) = 22,404; M_(w) = 26,916; M_(n) =11,257; PDI = 2.39 209 51 2.32 3.1 M_(p) = 14,689; M_(w) = 17,651; 77.8M_(n) = 4,327; PDI = 2.29 210 52 0.087 a Dual UV/RI. a UV: M_(p) =21,556; M_(w) = 47,428; M_(n) = 6,142; PDI = 7.72; RI: M_(p) = 40,121;M_(w) = 40,676; M_(n) = 18,309; PDI = 2.22 211 53 9.41 2.9 (¹³C) M_(p) =485; M_(w) = 1,035; 84.2 (¹³C) M_(n) = 317; PDI = 3.27 212 56 0.49 DualUV/RI. UV: M_(p) = 2,195 and 75; M_(w) = 1,301,735; M_(n) = 3,351; PDI =388.41; RI: M_(p) = 2,652; M_(w) = 84,063; M_(n) = 3,608; PDI = 23.30213 57 2.94 M_(p) = 9,779; M_(w) = 12,435; M_(n) = 4,519; PDI = 2.75 21458 7.77 1.7 Dual UV/RI. 60.3 UV: M_(p) = 21,192; M_(w) = 201,274; M_(n)= 10,087; PDI = 19.95; RI: M_(p) = 22,402; M_(w) = 95,991; M_(n) =11,047; PDI = 8.69 215 61 5.77 2.4 M_(p) = 9,535; M_(w) = 11,659; 56.1M_(n) = 4,357; PDI = 2.68 Examples 216-221 below include 20 equiv ofB(C₆F₅)₃ 216 71 3.45 0.6 M_(p) = 20,054; M_(w) = 19,855; 63.4 M_(n) =9,070; PDI = 2.19 217 72 1.32 1.6 M_(p) = 14,328; M_(w) = 16,242; 66.2M_(n) = 6,327; PDI = 2.57 218 73 0.27 219 69 1.79 1.5 Dual UV/RI. 62.1UV: M_(p) = 15,033; M_(w) = 21,410; M_(n) = 6,666; PDI = 3.21; RI: M_(p)= 8,520; M_(w) = 16,322; M_(n) = 2,159; PDI = 7.56 220^(b) 45 7.50 1.0M_(p) = 13,125; M_(w) = 14,026; 51.0 M_(n) = 6,211 PDI = 2.26 221^(c) 553.07 1.3 M_(p) = 7,458; M_(w) = 10,026; 58.2 M_(n) = 3,566; PDI = 2.81

[0377] TABLE 29 Effect of Pressure on Ethylene/EGPEA Copolymerizations(0.02 mmol Cmpd, 120° C., 18 h, 8 mL TCB, 2 mL EGPEA, 40 equiv B(C₆F₅)₃)Acrylate Press. Incorp. Total Ex. Cmpd MPa Yield g mol % M.W. Me 222 456.9 12.47 1.4 M_(p) = 12,036; M_(w) = 12,662; 51.8 M_(n) = 4,449; PDI =2.85 223 45 4.1 4.30 2.9 M_(p) = 7,492; M_(w) = 11,174; 57.7 M_(n) =3,738; PDI = 2.99 224 47 6.9 4.10 2.0 M_(p) = 8,181; M_(w) = 9,903; 59.9M_(n) = 3,243; PDI = 3.05 225 47 4.1 0.70 3.3 Dual UV/RI. 59.8 UV: M_(p)= 8,392; M_(n) = 4,579; M_(w) = 174,212; PDI = 38.05; RI: M_(p) = 9,874;M_(n) = 5,504; M_(w) = 18,139; PDI = 3.30

[0378] TABLE 30 ¹³C NMR Branching Analysis for EGPEA Copolymers Hex+ &Am+ & Bu+ & Me_(sBu) Me_(sBu) Ex. Total Me Me Et Pr Bu eoc eoc eoc (%)(%) 151 51.4 32.2 6.5 2.8 2.1 5.5 7.3 9.9 3.68 19.86 158 42.6 23.7 6.93.8 2.1 4.6 8.1 8.3 Nd Nd 169 27.3 19.0 1.7 1.7 1.0 3.2 3.4 4.8 Nd Nd159 26.1 17.7 2.9 1.2 1.0 1.9 2.5 4.2 Nd Nd 160 20.6 14.2 2.0 1.6 0.92.0 3.8 2.8 Nd Nd 211 84.2 36.9 10.2 3.1 4.1 21.8 31.0 34.0 9   54.8 199 72.0 45.1 6.2 3.3 4.3 7.8 13.4 17.4 Nd Nd

[0379] TABLE 31 ¹³C NMR Branching Analysis for MA Copolymers Hex+ & Am+& Bu+ & Me_(sBu) Me_(sBu) Ex. Total Me Me Et Pr Bu eoc eoc eoc (%) (%)167 78.2 45.2 9.9 4.1 4.7 9.8 14.5 19.0 4.4 19.9 166 72.0 41.7 10.0 3.98.5 11.9 16.3 4.2 18.9 165 76.0 42.7 11.0 4.0 8.7 12.8 18.3 5.8 23.1 25052.2 30.1 8.0 2.4 2.8 6.2 8.4 11.7 Nd Nd 251 62.4 35.1 8.7 3.6 4.6 7.411.3 15.0 Nd Nd 252 65.5 39.1 8.5 2.6 3.8 7.7 12.7 15.3 Nd Nd 253 79.644.9 11.1 3.4 4.1 10.0 14.7 20.1 Nd Nd 254 61.9 47.5 9.0 3.6 5.0 8.914.0 1.8 Nd Nd 255 35.7 23.1 4.2 1.9 1.4 3.0 5.8 6.9 Nd Nd 256 43.9 27.15.5 2.6 1.9 4.4 6.4 8.7 Nd Nd

[0380] TABLE 32 ¹³C NMR Branching Analysis for HA Copolymers Total AM+ &Bu+ & Me_(sBu) Me_(sBu) Ex. Me Me Et Pr Bu eoc eoc (%) (%) 154 53.2 27.55.3 3.1 2.8 16.4 17.3 trace trace 163 54.7 29.4 6.4 3.5 3.3 13.4 15.43.8 14.2 155 54.9 32.2 6.4 3.0 2.2 13.6 13.3 Nd Nd 253 32.8 22.1 3.2 1.51.1 6.2 6.0 Nd Nd 257 23.9 16.7 1.7 1.5 1.8 5.9 4.0 Nd Nd 258 28.3 19.73.2 1.4 1.4 3.7 4.0 Nd Nd

[0381] TABLE 33 ¹³C NMR Branching Analysis for THA Copolymers Hex+ & Am+& Bu+ & Me_(sBu) Me_(sBu) Ex. Total Me Me Et Pr Bu eoc eoc eoc (%) (%)184 34.0 22.7 3.2 2.3 1.8 3.7 4.1 5.8 3.3 15.7

[0382] TABLE 34 Effect of Counterion on Ethylene/EGPEA CopolymerizationsUsing Cmpd 45 (0.02 mmol Cmpd, 6.9 MPa E, 100° C., 18 h, 9 mL TCB, 1 mLEGPEA, 20 equiv B(C₆F₅)₃) Acrylate Incorp. Total Ex. Counterion Yield gmol % M.W. Me 226 [B[3,5-C₆H₃— 7.55 0.7 M_(p) = 24,874; M_(w) = 27,982;46.4 (CF₃)₂]₄]⁻ M_(n) = 11,277; PDI = 2.48 227 [B(C₆F₅)₄]⁻ 5.41 0.9M_(p) = 18,648; M_(w) = 20,469; 44.3 M_(n) = 8,130; PDI = 2.52

[0383] TABLE 35 Effect of Solvent on Ethylene/EGPEA CopolymerizationsUsing Cmpd 45 (0.02 mmol Cmpd, 6.9 MPa E, 100° C., 18 h, 9 mL Solvent, 1mL EGPEA, 20 equiv B(C₆F₅)₃) Acrylate Incorp. Total Ex. Solvent Yield gmol % M.W. Me 228 TCB 7.55 0.7 M_(p) = 24,874; M_(w) = 27,982; 46.4M_(n) = 11,277; PDI = 2.48 229 p-Xylene 11.32 0.6 M_(p) = 21,849; M_(w)= 21,579; 52.7 M_(n) = 9,271; PDI = 2.33 230 2,2,4-Trimethyl- 2.04 1.6M_(p) = 12,625; M_(w) = 13,906; 44.3 pentane M_(n) = 5,591; PDI = 2.74231 FC-75 1.04 5.4 M_(p) = 1,837; M_(w) = 3,468; 18.7 M_(n) = 1,265; PDI= 2.74

[0384] TABLE 36 Effect of B(C₆F₅)₃and NaBAF Concentrations onEthylene/EGPEA Copolymerizations Using Cmpd 45 (0.02 mmol Cmpd, 6.9 MPaE, 100° C., 18 h, 8 mL TCB, 2 mL of EGPEA) Acrylate B(C₆F₅)₃ NaBAFIncorp. Total Ex. equiv equiv Yield g mol % M.W. Me 232 40 20 7.53 1.2M_(p) = 16,054; M_(w) = 19,338; 38.6 M_(n) = 8,066; PDI = 2.40 233 40 105.38 1.3 M_(p) = 17,925; M_(w) = 18,882; 27.5 M_(n) = 8,495; PDI = 2.22234 20 10 7.01 1.5 M_(p) = 17,546; M_(w) = 18,485; 29.6 M_(n) = 7,769;PDI = 2.38 235 20 10 6.29 1.2 M_(p) = 14,365; M_(w) = 16,722; 29.5 M_(n)= 6,646; PDI = 2.52 236^(a) 20 10 4.69 1.3 M_(p) = 16,912; M_(w) =18,207; 33.6 M_(n) = 7,126; PDI = 2.57

[0385] TABLE 37 Effect of Solvent on Ethylene/Acrylate CopolymerizationsUsing Cmpd 45 (0.02 mmol Cmpd, 6.9 MPa, 100° C., 18 h, 8 mL Solvent, 2mL of EGPEA) Acrylate B(C₆F₅)₃ NaBAF Yield Incorp. Total Ex. Solventequiv equiv g mol % M.W. Me 237 TCB 40 20 7.53 1.2 M_(p) = 16,054; M_(w)= 19,338; 38.6 M_(n) = 8,066; PDI = 2.40 238 TCB 20 10 7.01 1.5 M_(p) =17,546; M_(w) = 18,485; 29.6 M= 7,769; PDI = 2.38 239 Toluene 40 20 6.051.0 M_(p) = 14,852; M_(w) = 16,995; 48.2 M_(n) = 7,853; PDI = 2.16 2402,2,4-Tri- 40 20 1.51 1.7 M_(p) = 6,633; M_(w) = 7,942; 41.8 methyl-M_(n) = 4,157; PDI = 1.91 pentane 241 2,2,4-Tri- 40 20 2.09 1.3 M_(p) =12,923; M_(w) = 16,462; 42.7 methyl- M_(n) = 6,313; PDI = 2.61 pentane242 Chloro- 20 10 9.16 1.0 M_(p) = 16,417; M_(w) = 18,316; 33.3 benzeneM_(n) = 7,496; PDI = 2.44 243 p-Xylene 20 10 7.46 1.0 M_(p) = 16,975;M_(w) = 18,211; 33.1 M_(n) = 7,246; PDI = 1.84

[0386] TABLE 38 Effect of Acrylate Concentration, Acrylate Structure andTemperature on Ethylene/Acrylate Copolymerizations (0.02 mmol Cmpd, 6.9MPa E, 18 h, 10 mL Total of TCB + Acrylate, 20 equiv B(C₆F₅)₃) AcrylateAcrylate Temp Yield Incorp. Total Ex. Cmpd mL ° C. g mol % M.W. Me 24445 EGPEA 100 7.55 0.7 M_(p) = 24,874; M_(w) = 27,982; 46.4 1 M_(n) =11,277; PDI = 2.48 245 45 EGPEA  80 2.20 0.6 M_(p) = 38,136; M_(w) =39,514; 49.6 1 M_(n) = 20,849; PDI = 1.90 246 45 EGPEA  80 5.41 0.4M_(p) = 45,864; M_(w) = 45,281; 81.7 0.5 M_(n) = 23,339; PDI = 1.94 24745 HA 100 5.68 0.66 (¹³C) M_(p) = 22,173; M_(w) = 21,451; 32.8 1 M_(n) =9,298; PDI = 2.31 (¹³C) 248 45 HA  80 1.65 1.0 M_(p) = 27,677; M_(w) =29,086; 26.3 1 M_(n) = 12,715; PDI = 2.29 249 47 EGPEA  80 0.08 0.8M_(p) = 17,915; M_(w) = 17,005; 51.4 1 M_(n) = 6,567; PDI = 250 45 MA100-135 10.58 0.31 (¹³C) M_(p) = 28,080; M_(w) = 21,336; 52.1 0.25 M_(n)= 4,233; PDI = 5.04 251 45 MA 100-135 8.36 0.51 (¹³C) M_(p) = 20,078;M_(w) = 17,262; 62.1 0.5 M_(n) = 3,831; PDI = 4.51 252 47 MA 100-1353.61 0.57 (¹³C) M_(p) = 4,716; M_(w) = 6,741; 65.1 0.25 M_(n) = 1,796;PDI = 3.75 253 47 MA 100-135 1.90 0.61 (¹³C) Dual UV/RI 78.8 0.5 UV:M_(p) = 3,803; M_(w) = 5,095; M_(n) = 1,350; PDI = 3.77; RI: M_(p) =5,237; M_(w) = 6,717; M_(n) = 3,805; PDI = 2.39 254 57 MA 100-135 4.220.37 (¹³C) M_(p) = 8,697; M_(w) = 14,347; 61.5 0.25 M_(n) = 3,656; PDI =3.92 10 equiv of NaBAF was added to Ex. 255 below and 20 equiv of NaBAFwere added to entries 256-261 below. 255 45 MA 100 4.28 1.09 (¹³C) M_(p)= 13,677; M_(w) = 15,046; 35.7 0.5 M_(n) = 7,270; PDI = 2.07 256 45 MA100 9.36 0.53 (¹³C) M_(p) = 16,828; M_(w) = 17,679; 43.7 0.5 M_(n) =7,546; PDI = 2.34 257 45 HA 100 1.07 1.20 (¹³C) M_(p) = 8,501; M_(w) =9,737; 23.9 2 M_(n) = 4,703; PDI = 2.07 258 45 HA 100 4.76 0.53 (¹³C)M_(p) = 16,421; M_(w) = 17,244; 28.3 1 M_(n) = 7,900; PDI = 2.18 259 45EGPEA 135 1.20 1.1 M_(p) = 7,174; M_(w) = 8,652; 74.9 2 M_(n) = 3,719;PDI = 2.33 260 45 EGPEA 130 5.59 1.2 M_(p) = 9,545; M_(w) = 10,772; 58.22 M_(n) = 4,927; PDI = 2.19 261 45 EGPEA 120 7.01 1.5 M_(p) = 17,546;M_(w) = 18,485; 29.6 2 M_(n) = 7,769; PDI = 2.38

[0387] TABLE 39 Effect of alpha-Diimine Structure on Ethylene/EGPEACopoly- merization (0.02 mmol Cmpd, 6.9 MPa E, 100° C. 18 h, 9 mL TCB, 1mL EGPEA, 20 equiv B(C₆F₅)₃) Acrylate Incorp. Ex. Cmpd Yield g mol %M.W. Total Me 262 55 7.55 0.7 M_(p) = 24,874; 46.4 M_(w) = 27,982; M_(n)= 11,277; PDI = 2.48 263 68 0.32 0.5 M_(p) = 13,743; 60.3 M_(w) =18,058; M_(n) = 5,435; PDI = 3.32 264 69 1.48 0.3 M_(p) = 838; 57.5M_(w) = 1,731; M_(n) = 796; PDI = 2.17

[0388] TABLE 40 Effect of alpha-Diimine Structure on Ethylene/AcrylateCo-polymerizations (0.02 mmol Cmpd, 6.9 MPa E, 18 h, 8 mL TCB, 2 mL ofEGPEA) Acrylate Temp B(C₆F₅)₃ NaBAF Yield Incorp. Total Ex. Cmpd (° C.)(equiv) (equiv) (g) (mol %) M.W. Me 265 45 100 40 20 7.53 1.2 M_(p) =16,054; M_(w) = 19,338; 38.6 M_(n) = 8,066; PDI = 2.40 266 76 100 40 204.22 1.0 M_(p) = 24,124; M_(w) = 27,307; 31.4 M_(n) = 14,435; PDI = 1.89267 75 100 40 20 5.68 1.2 M_(p) = 14,987; M_(w) = 16,393; 79.2 M_(n) =6,919; PDI = 2.37 268 74 100 40 20 3.42 0.6 M_(p) = 31,607; M_(w) =34,104; 41.2 M_(n) = 17,087; PDI = 2.00 269 77 100 40 20 0.025 1.9M_(n)(¹H): No olefins detected 33.5 270 45 135 20 10 1.20 1.1 M_(p) =7,174; M_(w) = 8,652; 74.9 M_(n) = 3,719; PDI = 2.33 271 64 135 20 101.05 0.5 M_(p) = 25,027; M_(w) = 30,553; 111.4 M_(n) = 12,666; PDI =2.41 272 45 135 20 10 2.55 1.0 M_(p) = 6,743; M_(w) = 8,241; 85.8 M_(n)= 887; PDI = 9.29

[0389] TABLE 41 Effect of Borone Concentration and Inhibitor on Ethyl-ene/EDPEA Copolymerizations (0.02 mmol Cmpd 45, 6.9 MPa E, 120° C., 18h, 6 mL TCB, 4 mL EGPEA) Acrylate In- B(C₆F₅)₃ Yield corp. % Ester inTotal Ex. equiv Inhibitor g mol % Copolymer^(a) M.W. Me 273 40 None 5.372.70 (¹³C) 12% M_(p) = 6,623; 42.6 M_(w) = 9,878; (^(—)C) M_(n) = 3,388;PDI = 2.92 274 20 NaBAF 3.02 2.2 20% M_(p) = 12,928; 28.4 20 equiv M_(w)= 13,956; M_(n) = 5,371; PDI = 2.60 275 20 BQ 250 2.59 2.6 16% M_(p) =8,739; 27.5 ppm M_(w) = 10,424; M_(n) = 3,480; PDI = 3.00 276 20 NaBAF3.07 2.4 23% M_(p) = 11,454; 29.9 20 equiv M_(w) = 12,303; BQ 250 M_(n)= 4,114; ppm PDI =

[0390] TABLE 42 Steric Effects on Ethylene/MA CopolymerizationsUtilizing Long Reaction Times (90 h) and Low Catalyst Concentrations(0.019 mmol Cmpd), (211 equivB(C₆F₅)_(3 and 105 equiv NaBAF were used. Mole % incorp. and) total Medetermined by ¹³C NMR spectroscopy.) MA mL Acrylate (p-Xylene Press TempYield Incorp Total Ex Cmpd mL) MPa ° C. g mol % M.W. Me 277 45 0.5 3.5120 0.892 1.33 M_(p) = 6,812; M_(w) = 7,201; 72.5 (9.5) M_(n) = 3,410;PDI = 2.05 278 76 0.5 3.5 120 0.937 1.02 M_(p) = 7,911; M_(w) = 8,993;82.7 (9.5) M_(n) = 4,499; PDI = 2.00 279 74 0.5 3.5 120 0.840 0.93 M_(p)= 8,726; M_(w) = 9,799; 94.9 (9.5) M_(n) = 4,511; PDI = 2.00 280 64 0.53.5 120 0.106 nd M_(p) = 13,521; M_(w) = 14,744; nd (9.5) M_(n) = 6,125;PDI = 2.41 281 45 1.0 3.5 120 0.007 nd nd nd (14.0)  282 45 0.5 6.9 1203.340 0.82 M_(p) = 12,403; M_(w) = 13,853; 50.4 (9.5) M_(n) = 5,681; PDI= 2.44 283 76 0.5 6.9 120 4.221 0.48 M_(p) = 20,376; M_(w) = 20,960;58.1 (9.5) M_(n) = 9,659; PDI = 2.17 284 74 0.5 6.9 120 5.424 0.43 M_(p)= 28,364; M_(w) = 30,997; 68.5 (9.5) M_(n) = 12,568; PDI = 2.47 285 640.5 6.9 120 0.95 0.30 M_(p = 47,858; M) _(w) = 47,408; 97.2 (9.5) M_(n)= 20,796; PDI = 2.28 286 45 1.0 6.9 120 2.518 0.97 M_(p) = 13,043; M_(w)= 14,076; 46.3 (14.0)  M_(n) = 5,931; PDI = 2.37 287 45 0.5 6.9 1003.865 0.62 M_(p) = 23,142; M_(w) = 24,270; 30.9 (9.5) M_(n) = 10,544;PDI = 2.30 288 76 0.5 6.9 100 3.720 0.45 M_(p) = 34,987; M_(w) = 36,412;37.4 (9.5) M_(n) = 16,929; PDI = 2.15 289 74 0.5 6.9 100 4.041 0.51M_(p) = 53,630; M_(w) = 50,877; 48.0 (9.5) M_(n) = 24,819; PDI = 2.05290 64 0.5 6.9 100 0.860 0.50 M_(p) = 64,690; M_(w) = 60,660; 78.1 (9.5)M_(n) = 31,328; PDI = 1.94 291 45 1.0 6.9 100 1.631 0.83 M_(p) = 17,935;M_(w) = 17,277; 35.7 (14.0)  M_(n = 7,070; PDI = 2.44)

[0391] TABLE 43 ¹³C NMR Branching Analysis for MA Copolymers of Table 42Ex. Total Me Me Et Pr Bu Hex+ & eoc Am+ & eoc Bu+ & eoc 277 72.5 42.610.0 3.8 3.9 7.1 13.1 16.2 58.7% 13.8% 5.2% 5.4% 9.8% 18.1% 22.4% 27882.7 48.9 10.3 4.4 4.2 10.3 15.0 19.2 59.1% 12.5% 5.3% 5.0% 12.5% 18.2%23.2% 279 94.9 54.5 13.4 5.2 5.3 12.7 17.0 21.8 57.5% 14.1% 5.5% 5.6%13.4% 18.0% 22.9% 282 50.4 32.0 5.7 2.6 2.5 6.7 8.3 10.0 63.6% 11.4%5.2% 5.0% 13.3% 16.5% 19.8% 283 58.1 37.5 6.6 3.0 2.7 6.3 8.8 11.1 64.5%11.3% 5.1% 4.7% 10.8% 15.1% 19.1% 284 68.5 44.4 6.9 3.5 3.3 7.1 10.113.6 64.8% 10.1% 5.1% 4.8% 10.4% 14.7% 19.9% 285 97.2 65.4 10.0 4.1 4.19.4 13.3 17.8 67.3% 10.3% 4.2% 4.2% 4.6% 13.7% 18.3% 286 46.3 29.6 5.12.4 1.9 5.2 6.7 9.2 64.0% 11.0% 5.1% 4.0% 11.3% 14.5% 19.9% 287 30.920.4 4.1 1.4 1.0 2.7 3.7 5.0 66.0% 13.3% 4.6% 3.1% 8.7% 12.0% 16.1% 28837.4 24.0 4.8 1.9 1.1 3.8 4.6 6.8 64.2% 12.8% 5.0% 3.1% 10.1% 12.2%18.1% 289 48.0 32.6 4.7 2.5 1.7 4.5 5.9 8.3 67.9% 9.7% 5.1% 3.6% 9.5%12.3% 17.3% 290 78.1 53.9 7.3 3.3 3.1 7.7 10.6 13.7 69.0% 9.3% 4.2% 3.9%9.9% 13.5% 17.5% 291 35.7 23.2 4.0 1.7 1.8 4.4 5.4 6.8 35.7% 11.1% 4.7%5.2% 12.4% 15.0% 19.1%

[0392] TABLE 44 Ethylene/EGPEA Copolymerizations in Chlorobenzene (18 h,10 mL Total Volume of Chlorobenzene + EGPEA) Acrylate Cmpd EGPEAB(C₆F₅)₃ NaBAF Press Temp Yield Incorp Total Ex. mmol mL equiv equiv MPa° C. g mol % M.W. Me 292 45 0.01 1 40 20 6.9 100 10.28 0.4 M_(p) =22,374; M_(w) = 23,126; M_(n) = 10,630; PDI = 2.18 49.5 293 45 0.005 180 40 6.9 100 7.84 0.5 M_(p) = 26,320; M_(w) = 26,956; M_(n) = 12,371;PDI = 2.18 82.7 294 64 0.005 1 80 40 6.9 100 1.85 0.4 M_(p) = 83,096;M_(w) = 81,919; M_(n) = 39,427; PDI = 2.08 71.5 295 55 0.005 1 80 40 6.9100 1.87 0.7 M_(p) = 22,984; M_(w) = 24,347; M_(n) = 12,365; PDI = 1.9741.3 296 45 0.01 1 40 20 3.5 120 5.59 0.6 M_(p) = 9,544; M_(w) = 10,892;M_(n) = 4,896; PDI = 1.97 73.5 297 64 0.01 1 40 20 3.5 120 0.78 0.4M_(p) = 26,286; M_(w) = 26,534; M_(n) = 13,114; PDI = 2.02 134.2 298 550.01 1 40 20 3.5 120 1.97 M_(p) = 7,250; M_(w) = 8,005; M_(n) = 3,348;PDI = 2.39 299 45 0.01 1 40 20 6.9 120 12.49 0.6 M_(p) = 14,470; M_(w) =15,044; M_(n) = 6,519; PDI = 2.31 70.6 300 45 0.01 2 40 20 6.9 120 6.011.5 M_(p) = 11,778; M_(w) = 12,804; M_(n) = 5,707; PDI = 2.24 61.2 30145 0.01 3 40 20 6.9 120 4.14 2.4 M_(p) = 7,806; M_(w) = 10,643; M_(n) =4,312; PDI = 2.47 48.6 302 45 0.005 1 80 40 6.9 120 7.29 0.6 M_(p) =11,733; M_(w) = 13,519; M_(n) = 5,644; PDI = 2.40 67.2 303 45 0.005 2 8040 6.9 120 5.07 1.4 M_(p) = 9,852; M_(w) = 11,599; M_(n) = 4,755; PDI =2.44 67.1 304 78 0.02 2 20 10 6.9 120 0.96 1.4^(a) M_(p) = 30,063; M_(w)= 25,126; M_(n) = 7,262; PDI = 3.46 28.0 305 78 0.02 4 20 10 6.9 1201.06 1.1^(a) M_(p) = 4,852; M_(w) = 6,734; M_(n) = 2,384; PDI = 2.8212.5 306 45 0.005 1 80 40 3.5 120 2.64 0.8 M_(p) = 10,797; M_(w) =11,715; M_(n) = 5,047; PDI = 2.32 66.8 307 45 0.005 2 80 40 3.5 120 2.951.9 M_(p) = 8,636; M_(w) = 9,312; M_(n) = 4,496; PDI = 2.07 67.6 308 450.01 2 40 20 3.5 120 2.96 1.2 M_(p) = 7,616; M_(w) = 8,630; M_(n) =3,709; PDI = 2.33 66.3 309 45 0.01 3 40 20 3.5 120 2.70 1.9 M_(p) =5,039; M_(w) = 7,443; M_(n) = 2,709; PDI = 2.75 59.0 310 45 0.0025 1 16080 3.5 120 1.59 0.9 M_(p) = 7,737; M_(w) = 8,732; M_(n) = 4,051; PDI =2.16 73.0 311 45 0.0025 1 160 80 6.9 100 2.52 0.8 M_(p) = 25,609; M_(w)= 25,456; M_(n) = 11,960; PDI = 2.13 27.5 312 45 0.0025 2 160 80 6.9 1002.02 2.1 M_(p) = 20,773; M_(w) = 21,386; M_(n) = 10,385; PDI = 2.06 22.1313 45 0.0025 0.5 160 80 6.9 100 5.85 trace M_(p) = 23,609; M_(w) =25,970; M_(n) = 12,143; PDI = 2.14 nd 314 45 0.00125 1 160 80 6.9 1001.67 1.0 M_(p) = 22,495; M_(w) = 23,371; M_(n) = 11,316; PDI = 2.07 27.4315 45 0.00125 1 160 80 6.9 120 2.96 0.9 M_(p) = 12,729; M_(w) = 13,757;M_(n) = 6,189; PDI = 2.22 68.2 316 45 0.0025 0.5 160 80 6.9 120 7.27 0.4M_(p) = 13,244; M_(w) = 15,491; M_(n) = 6,318; PDI = 2.45 70.8 317 450.0025 2 160 80 6.9 120 3.22 1.5 M_(p) = 12,047; M_(w) = 13,044; M_(n) =6,043; PDI = 2.16 55.6 318 45 0.0025 1 160 80 6.9 120 5.02 0.7 M_(p) =12,942; M_(w) = 13,493; M_(n) = 6,073; PDI = 2.22 58.7

[0393] TABLE 45 Ethylene/EGPEA Copolymerizations in TCB: Variation ofCatalyst Concentration and Structure, and Temperature(6.9 MPa E, 18 h,10 mL Total Volume of TCB + EGPEA) Acrylate Cmpd EGPEA B(C₆F₅)₃ NaBaFTemp Yield Incorp Total Ex. mmol mL equiv Equiv ° C. g mol % M.W. Me 31945 1 40 20 140 3.01 0.5 M_(p) = 7,507; 87.5 0.01  M_(w) = 8,668; M_(n) =3,753; PDI = 2.31 320 45 2 40 20 140 2.43 1.6 M_(p) = 6,568; 80.8 0.01 M_(w) = 7,865; M_(n) = 3,535; PDI = 2.22 321 45 1 80 40 140 2.41 0.7M_(p) = 7,192; 88.7 0.005 M_(w) = 8,650; M_(n) = 3,909; PDI = 2.21 32245 2 80 40 140 1.66 1.6 M_(p) = 6,197; 82.0 0.005 M_(w) = 7,988; M_(n) =3,234; PDI = 2.47 323 45 1 160 80 140 4.54 0.7 M_(p) = 7,443; 91.6 0.0025 M_(w) = 8,725; M_(n) = 3,328; PDI = 2.62 324 96 1 20 10 120 2.141.2 M_(p) = 9,128; 120.9 0.02  M_(w) = 12,153; M_(n) = 5,089; PDI = 2.39325 97 1 20 10 120 1.79 0.6 M_(p) = 56,495; 18.0 0.02  M_(w) = 56,319;M_(n) = 25,240; PDI = 2.23

[0394] TABLE 46 Ethylene/MA Copolymerizations: Variation of Temperature(0.0024 mmol Cmpd, 160 equiv B(C₆F₅)₃, 80 equiv NaBAF, 6.9 MPa E, 18 h0.5 mL NA, 9.5 mL Chlorobenzene) Acrylate Temp Yield Incorp Total ExCmpd ° C. g Mol % M.W. Me 326 45 100 2.90 0.53 (^(—)C) M_(p) = 17,308;M_(w) = 18,706; M_(n) = 9,144; 31.8 PDI = 2.05 327 45 120 2.59 0.45(^(—)C) M_(p) = 9,967; M_(w) = 10,394; M_(n) = 4,713; 51.8 PDI = 2.21

[0395] TABLE 47 ¹³C NMR Branching Analysis for MA and HA Copolymers ofTables 46, 49 and 50 Total Hex+ & Am+ & Bu+ & Ex. Me Me Et Pr Bu eoc eoceoc 326 31.8 21.3 3.6 1.6 1.6 2.9 4.7 5.3 327 51.8 31.6 5.8 13.1 2.6 4.88.9 11.2 346 71.7 45.2 7.6 3.7 3.4 6.2 11.0 15.2 347 71.8 45.9 7.8 3.83.8 6.5 11.1 14.4 354 48.6 29.7 6.1 2.9 2.6 3.7 6.9 9.9 364 58.5 36.57.8 2.7 2.8 9.6 11.6 366 60.2 36.0 7.9 3.4 2.6 5.7 9.5 12.8 383 31.122.0 3.5 1.2 1.6 2.8 4.0 4.5 384 28.5 19.1 2.6 1.6 1.4 2.0 4.4 5.3 38898.6 68.1 12.2 2.5 2.8 11.2 12.1 15.8

[0396] TABLE 48 Ethylene/EGPEA Copolymerizations: Variation of CatalystStructure and Cocatalyst Concentration (18 h, 6.9 MPa E, 120° C., 0.5 mLEGPEA) Acrylate Cmpd Solvent B(C₆F₅)₃ NaBAF Yield Incorp M.W. Total Ex.mmol mL equiv Equiv g mol % M.W. Me 328 45 CB 320 160 1.80 0.4 M_(p) =13,525; M_(w) = 13,741; 59.8 0.00125 9.5 M_(n) = 6,126; PDI = 2.24 32945 CB 640 160 3.72 0.3 M_(p) = 11,892; M_(w) = 13,222; 61.6 0.00125 9.5M_(n) = 6,184; PDI = 2.14 330 45 CB 1600  160 2.90 0.4 M_(p) = 11,920;M_(w) = 12,850; 65.3 0.00125 9.5 M_(n) = 6,419; PDI = 2.00 331 45 CB 320320 3.05 0.3 M_(p) = 12,013; M_(w) = 12,568; 66.8 0.00125 9.5 M_(n) =5,783; PDI = 2.17 332 45 Toluene 320 160 3.52 0.3 M_(p) = 10,810; M_(w)= 12,116; 65.4 0.00125 9.5 M_(n) = 5,518; PDI = 2.20 333 45 CB 320 1601.47 0.7 M_(p) = 13,399; M_(w) = 14,553; 53.4 0.00125 4.5 M_(n) = 7,141;PDI = 2.04 334 61 CB 320 160 1.70 0.4 M_(p) = 6,206; M_(w) 7,385;65.70.0025  9.5 M_(n) = 3,287; PDI = 2.25 335 57 CB 320 160 0.76 0.3 M_(p) =15,079; M_(w) = 15,975; 68.5 0.0025  9.5 M_(n) = 8,241; PDI = 1.94 33674 CB 320 160 3.58 0.2 M_(p) = 29,889; M_(w) = 34,141; 72.6 0.0025  9.5M_(n) = 17,674; PDI = 1.93 337 71 CB 320 160 0.055 0.2 M_(p) = 13,750;M_(w) = 15,066; 91.2 0.0025 9.5 M_(n) = 7,535; PDI = 2.00

[0397] TABLE 49 Ethylene/Acrylate Copolymerizations: Variation ofCatalyst Structure, Catalyst and Cocatalyst Concentration (18 h, 6.9 MPaE, 120° C.) Acrylate Cmpd Solvent/mL B(C₆F₅)₃ NaBAF Yield Incorp Ex.mmol Acrylate/mL Equiv equiv g mol % M.W. Me 338 45, 0.00125 CB/9,EGPEA/1 640 160 1.79 0.6 M_(p) = 11,857; M_(w) = 12,974; M_(n) = 5,887;PDI = 2.20 59.4 339 45, 0.0025 CB/14, EGPEA/1 640 160 3.47 0.4 M_(p) =11,853; M_(w) = 12,966; M_(n) = 5,513; PDI = 2.35 64.2 340 45, 0.00125CB/14, EGPEA/1 640 160 2.02 0.5 M_(p) = 12,305; M_(w) = 12,062; M_(n) =5,229; PDI = 2.31 67.1 341 45, 0.00125 CB/14, EGPEA/1 960 320 2.26 0.4M_(p) = 11,788; M_(w) = 12,131; M_(n) = 5,524; PDI = 2.20 60.9 342 45,0.0025 CB/13, EGPEA/2 960 160 2.54 0.7 M_(p) = 10,220; M_(w) = 11,156;M_(n) = 5,349; PDI = 2.09 62.1 343 74, 0.00125 CB/14, EGPEA/1 960 1600.77 0.2 M_(p) = 29,720; M_(w) = 32,471; M_(n) = 17,281; PDI = 1.88 66.1344 74, 0.0025 CB/13, EGPEA/2 960 160 1.35 0.5 M_(p) = 26,232; M_(w) =27,641; M_(n) = 14,194; PDI = 1.95 69.6 345 74, 0.00125 Toluene/14,EGPEA/1 960 160 1.55 0.2 M_(p) = 30,222; M_(w) = 32,909; M_(n) = 18,006;PDI = 1.83 69.6 346 74, 0.00125 CB/14.5, MA/0.5 960 160 0.82 0.3 M_(p) =23,118; M_(w) = 23,916; M_(n) = 10,009; PDI = 2.39 71.7 (¹³C) (¹³C) 34774, 0.0025 CB/14, MA/1 960 160 1.32 0.4 M_(p) = 11,962; M_(w) = 13,390;M_(n) = 6,417; PDI = 2.09 71.8 (¹³C) (¹³C) 348 45, 0.00125 TCB/9.5,EGPEA/0.5 640 320 2.33 trace M_(p) = 14,132; M_(w) = 15,668; M_(n) =6,596; PDI = 2.38 nd 349 45, 0.00125 TCB/9, EGPEA/1 640 320 2.03 0.9M_(p) = 11,996; M_(w) = 13,748; M_(n) = 6,235; PDI = 2.21 51.9 350 45,0.0019 TCB/9.5, EGPEA/0.5 421 210 4.71 0.4 M_(p) = 13,326; M_(w) =15,974; M_(n) = 6,186; PDI = 2.58 57.4 351 45, 0.0019 TCB/9, EGPEA/1 421210 3.29 0.8 M_(p) = 11,534; M_(w) = 13,641; M_(n) = 5,635; PDI = 2.4260.2 352 45, 0.0019 TCB/9.5, EGPEA/0.5 210 210 4.43 0.4 M_(p) = 12,953;M_(w) = 13,730; M_(n) = 5,116; PDI = 2.68 nd 353 45, 0.0019p-Xylene/9.5, 421 210 5.62 0   M_(p) = 14,910; M_(w) = 32,190; M_(n) =8,859; PDI = 3.63 71.8 EGPEA/0.5 354 45, 0.0019 TCB/9.75, MA/0.25 421210 0.81 0.3 M_(p) = 11,398; M_(w) = 13,504; M_(n) = 5,827; PDI = 2.3248.6 (¹³C) (¹³C) 355 78, 0.01 TCB/9, EGPEA/1  80 40 0.59 Nd^(a) M_(p) =64,840; M_(w) = 57,576; M_(n) = 24,348; PDI = 2.36 nd 356 78, 0.01TCB/9, EGPEA/1  80 40 0.56 Nd^(a) M_(p) = 64,496; M_(w) = 59,869; M_(n)= 30,765; PDI = 1.95 nd 357 76, 0.0019 TCB/9.5, EGPEA/0.5 421 210 3.950.5 M_(p) = 21,762; M_(w) = 23,924; M_(n) = 12,118; PDI = 1.97 67.5 35845, 0.0019 TCB/9, EGPEA/1 421 210 3.74 0.6 M_(p) = 12,616; M_(w) =15,891; M_(n) = 6,055; PDI = 2.62 57.1 359 45, 0.0019 p-Xylene/8, Butyl421 210 1.24 0.7 M_(p) = 8,918; M_(w) = 9,634; M_(n) = 4,250; PD = 12.2762.8 Ether/1 EGPEA/1 360 45, 0.0019 p-Xylene/4.5, Butyl 421 210 0.91 0.8M_(p) = 6,913; M_(w) = 8,108; M_(n) = 4,024; PD= 12.02 67.6 Ether/4.5,EGPEA/1 361 45, 0.0019 Butyl Ether/9, EGPEA/1 421 210 0.97 1.0 M_(p) =6,100; M_(w) = 6,969; M_(n) = 3,626; PDI = 1.92 66.8 362 45, 0.00125p-Xylene/9, EGPEA/1 640 320 0.98 0.5 M_(p) = 21,762; M_(w) = 23,924;M_(n) = 12,118; PDI = 1.97 67.5 363 45, 0.00 19 TCB/9, HA/1 421 2100.025 Nd Nd Nd 364 45, 0.00125 p-Xylene/9, HA/1 640 320 2.53 0.6 M_(p) =11,816; M_(w) = 11,804; M_(n) = 5,225; PDI = 2.26 58.5 (¹³C) (¹³C) 36545, 0.0019 TCB/9.5, MA/0.5 421 210 0.083 Nd Nd Nd 366 45, 0.00125p-Xylene/9.5, MA/0.5 640 320 2.58  0.75 M_(p) = 10,362; M_(w) = 10,505;M_(n) = 5,123; PDI = 2.05 67.5 (¹³C) (¹³C) 367 79, 0.0019 TCB/9, EGPEA/1421 105 0.018 Nd Nd Nd 368 59, 0.0019 TCB/9, EGPEA/1 421 105 0.51 1.1M_(p) = 6,858; M_(w) = 7,745; M_(n) = 3,968; PDI = 1.95 47.2 369 80,0.0019 TCB/9, EGPEA/1 421 105 0.59 0.6 M_(p) = 11,196; M_(w) = 14,898;M_(n) = 6,228; PDI = 2.39 60.0 370 81, 0.0019 TCB/9, EGPEA/1 421 1050.004 Nd Nd Nd 371 45, 0.0019 p-Xylene/9, EGPEA/1 421 105 3.20 0.6 M_(p)= 14,259; M_(w) = 14,764; M_(n) = 6,250; PDI = 2.36 55.6 372 45,0.0019^(c) TCB/9, EGPEA/1 421 105 2.64 0.6 M_(p) = 13,840; M_(w) =15,593; M_(n) = = 7,075; PDI = 2.20 57.1 373 82, 0.0019 TCB/9, EGPEA/1421 105 0.32 Nd M_(p) = 35,840; M_(w) = 37,957; M_(n) = 20,356; PDI =1.86 Nd 374 45, 0.0019 TCB/9, EGPEA/1 421 105 0.18 2.0 M_(p) = 13,679;M_(w) = 15,497; M_(n) = 7,382; PDI = 2.10 60.4 375 45, 0.0019p-Xylene/9, EGPEA/1 421 105 0.86 1.2 M_(p) = 6,984; M_(w) = 8,147; M_(n)= 3,927; PDI = 2.07 55.6 376 64, 0.002 p-Xylene/3, EGPEA/2 200 100 0.25 4.2^(b) M_(p) = 13,668; M_(w) = 14,464; M_(n) = 6,967; PDI = 2.08 59.4377 64, 0.002 p-Xylene/8, EGPEA/2 200 100 0.76 3.1 M_(p) = 25,728; M_(w)= 26,593; M_(n) 13,836; PDI = 1.92 87.2 378 64, 0.002 p-Xylene/4.5,MA/0.5 200 100 0.52 2.3 M_(p) = 30,000; M_(w) = 31,999; M_(n) = 14,434;PDI = 2.22 98.6 (¹³C) (¹³C) 379 64, 0.002 p-Xylene/4.5, MA/0.5 800 1000.68 Nd M_(p) = 28,722; M_(w) = 31,214; M_(n) = 13,352; PDI = 2.34 Nd

[0398] TABLE 50 Ethylene/Acrylate Copolymerizations: Variation ofSolvent and Acrylate Substituent (18 h, 6.9 MPa E, 100° C.) AcrylateCmpd Solvent/mL B(C₆F₅)₃ NaBAF Yield Incorp Total Ex. mmol Acrylate/mLEquiv equiv g mol % M.W. Me 380 45 Toluene/9 421 105 1.28 1.1 M_(p) =20,773; 38.0 0.0019 EGPEA/1 M_(w) = 21,618; M_(n) = 10,131; PDI = 2.13381 45 Toluene/9 421 105 1.40 0.4 M_(p) = 20,340; 49.2 0.0019 HA/1 M_(w)= 20,560; M_(n) = 9,573; PDI = 2.15 382 45 CB/9 421 105 0.57 0.5 M_(p) =18,173; 43.4 0.0019 HA/1 M_(w) = 18,605; M_(n) = 8,670; PDI = 2.15 38345 Toluene/9.5 421 105 1.99 0.6 M_(p) = 20,997; 31.1 0.0019 MA/0.5 (¹³C)M_(w) = 21,705; (¹³C) M_(n) = 10,684; PDI = 2.03 384 45 CB/9.5 421 1051.33 0.4 M_(p) = 13,279; 28.5 0.0019 MA/0.5 M_(w) = 15,028; M_(n) =7,635; PDI = = 1.97

[0399] TABLE 51 Ethylene/Hexyl Acrylate Copolymerizations: Variation ofCatalyst Structure (18 h, 6.9 MPa E, 120° C., 1 mL Hexyl Acrylate, 9 mLp-Xylene) Acrylate Cmpd B(C₆F₅)₃ LiB(C₆F₅)₄ Yield Incorp Total Ex. 0.005mmol equiv equiv g mol % M.W. Me 385 79 80 40 1.92 1.3 M_(p) = 20,773;M_(w) = 21,618; 78.4 M_(n) = 10,131; PDI = 2.13 386 81 80 40 0.011 Nd NdNd 387 53 80 40 0.41 2.3 M_(p) = 782; M_(w) = 1,183; 98.4 M_(n) = 409;PDI = 2.89

[0400] TABLE 52 Ethylene/EGPEA Copolymerizations: Variation ofp-Substituent on the N-Aryl Ring (0.0019 mmol Cmpd, 18 h, 6.9 MPa E,120° C., 1 mL EGPEA, 9 mL TCB) Acrylate Cmpd B(C₆F₅)₃ LiB(C₆F₅)₄ YieldIncorp Total Ex. mmol equiv equiv g mol % M.W. Me 388 45 211 105 3.980.8 M_(p) = 14.113; M_(w) = 16,389; 53.2 M_(n) = 6,722; PDI = 2.44 38983 211 105 3.78 0.8 M_(p) = 15,156; M_(w) = 16,926; 54.4 M_(n) = 7,557;PDI = 2.24 390 84 211 105 2.80 1.1 M_(p) = 14,422; M_(w) = 15,390; 48.7M_(n) = 6,960; PDI = 2.21

[0401] TABLE 53 Ethylene/2,2,3,3,3-Pentafluoropropyl acrylate (PPA)Copolymerizations (0.0019 mmol Cmpd, 18 h, 10 mL Total Volume ofp-Xylene + PPA, 100° C., 6.9 MPa E) Acrylate PPA B(C₆F₅)₃ NaBAF YieldIncorp Total Ex. Cmpd mL equiv equiv g mol % M.W. Me 391 45 1 211 1055.93 0.2 M_(p) = 25,838; M_(w) = 26,041; 31.3 M_(n) = 10,736; PDI = 2.43392 74 1 211 105 4.09 0.3 M_(p) = 67,066; M_(w) = 64,176; 45.5 M_(n) =32,073; PDI = 2.00 393 45 2 211 105 3.76 0.3 M_(p) = 22,227; M_(w) =22,623; 28.6 M_(n) = 10,036; PDI = 2.25 394 74 2 211 105 3.36 0.3Bimodal: 48.4 M_(p) = 56,152; M_(w) = 49,560; M_(n) = 18,664; PDI = 2.66

[0402] TABLE 54 Ethylene/EGPEA Copolymerizations: Variation of CatalystStructure, Pressure and Temperature (18 h, 1 mL EGPEA, 9 mL p-Xylene,0.0019 mmol Cmpd, 211 equiv B(C₆F₅)₃, 105 equiv NaBAF Acrylate PressTemp Yield Incorp Total Ex. Cmpd MPa ° C. g mol % M.W. Me 395 85 3.5 800.016 trace Nd 396 86 3.5 80 0.437 0.8 M_(p) = 916; M_(w) = 1,670; 39.90.6 IC M_(n) = 739; PDI = 2.26 0.2 EG 397 87 3.5 80 0.429 2.1 M_(p) =26,655; M_(w) = 28,284; 31.1 M_(n) = 13,707; PDI = 2.06 398 88 3.5 800.203 2.2 M_(p) = 2,832; M_(w) = 3,358; 44.4 M_(n) = 1,754; PDI = 1.92399 89 3.5 80 0 —    — — 400 85 6.9 120 0.318 0.7 M_(p) = 327; M_(w) =1,150; 57.7 M_(n) = 305; PDI = 3.77 401 86 6.9 120 1.49 0.6, 0.4 M_(p)488; M_(w) = 864; 82.1 IC, 0.2 EG M_(n) = 364; PDI = 2.37 402 87 6.9 1203.14 0.5 M_(p) = 15,311; M_(w) = 15,880; 65.7 M_(n) = 7,213; PDI = 2.20403 88 6.9 120 0.565 1.1 M_(p) = 1,702; M_(w) = 2,418; 95.7 M_(n) =1,148; PDI = 2.11 404 89 6.9 120 0 —    — — 405 90 6.9 120 1.86 1.3M_(p) = 4,834; M_(w) = 5,311; 52.5 M_(n) = 2,530; PDI = 2.10 406 91 6.9120 0.50 1.6, 1.3 M_(p) = 1,382; M_(w) = 2,217; 78.4 IC, 0.3 EG M_(n) =982; PDI = 2.26 407 92 6.9 120 1.32 0.8 M_(p) = 22,852; M_(w) = 24,968;69.9 M_(n) = 12,472; PDI = 2.00 408 93 6.9 120 0 —    — — 409 94 6.9 1201.24 1.4 M_(p) = 4,172; M_(w) = 4,579; 60.8 M_(n) 2,254; PDI = 2.03 41095 6.9 120 0 —    — — 411 78 6.9 130 0.047 Nd^(b) M_(p) = 20,248; M_(w)= 20,678; Nd M_(n) = 7,869; PDI = 2.63 412 64 6.9 130 0.336 0.7 M_(p) =31,486; M_(w) 32,872; 108.5  M_(n) = 14,840; PDI = 2.22 413 74 6.9 1302.87 1.0, 0.7 M_(p) = 19,881; M_(w) 20,567; 97.0 IC, 0.3 EG M_(n) =8,185; PDI = 2.51

[0403] TABLE 55 Ethylene/EGPEA Copolymerizations: Variation of CatalystStructure, Cocatalyst Concentration, and Borate Counterion and Structure(0.0019 mmol Cmpd, 18 h, 2 mL EGPEA, 8 mL p-Xylene, 100° C., 6.9 MPa E)Acrylate B(C₆F₅)₃ Borate Yield Incorp Total Ex. Cmpd equiv 105 equiv Gmol % M.W. Me 414 74 211 NaBAF 0.746  3.4^(a) M_(p) = 28,528; M_(w) =29,829; 32.1 M_(n) = 11,409; PDI = 2.61 415 74 211 LiBArF 0.647 1.9M_(p) = 39,148; M_(w) = 36,313; 41.3 M_(n) = 14,745; PDI = 2.46 416 74421 NaBAF 0.217 1.3 M_(p) = 26,280; M_(w) = 27,880; 36.9 M_(n) = 13,106;PDI = 2.13 417 74 421 LiBArF 0.358 1.2 M_(p) = 33,089; M_(w) = 33,479;44.6 M_(n) = 15,943; PDI = 1.57 418 76 421 LiBArF 0.738 1.2 M_(p) =29,924; M_(w) = 29,685; 36.1 M_(n) = 12,971; PDI = 2.29 419 92 421LiBArF 0.385 1.1 M_(p) = 34,623; M_(w) = 35,775; 33.4 M_(n) = 18,240;PDI = 196 420 64 421 LiBArF 0.009 0.7 M_(n) (¹H): No olefins 58.8 421 93421 LiBArF 0.021 1.5 M_(n) (¹H): No olefins 33.2 422 96 421 LiBArF 0.109Nd Nd Nd 423 90 421 LiBArF 0.982 2.5 M_(p) = 7,599; M_(w) = 8,271; 26.3M_(n) = 3,746; PDI = 2.21 424 74 211 LiBArF 0.86 1.6 M_(p) = 26,306;M_(w) = 28,886; 37.6 M_(n) = 10,439; PDI = 2.77 425 74 105 LiBArF 1.232.2 M_(p) = 16,233; M_(w) = 21,189; 38.5 M_(n) = 8,573; PDI = 2.47 42674  53 LiBArF 4.75 0   M_(p) = 76,091; M_(w) = 76,631; Nd M_(n) =24,522; PDI = 3.13

[0404] TABLE 56 Ethylene/EGPEA Copolymerizations: Variation of CatalystStructure and Concentration (18 h, 1 mL EGPEA, 9 mL p-Xylene, 80° C.,6.9 MPa E) Acrylate Cmpd B(C₆F₅)₃ LiB(C₆F₅)₄ MeAl(BHT)₂ Yield IncorpTotal Ex. mmol equiv equiv equiv g mol % M.W. Me 427 59 40 20 0 6.73 1.6M_(p) = 21,259; 15.3 0.01  0.9 IC M_(w) = 21,724; 0.7 EG M_(n) = 10,233;PDI = 2.12 428 59 211 105 20 0.739 1.1 M_(p) = 19,634; 10.9 0.0019 M_(w)= 20,285; M_(n) = 8,383; PDI = 2.42 429 94 40 20 0 3.87 1.3 M_(p) =11,047; 24.5 0.01  0.910 M_(w) = 11,998; 0.4 EG M_(n) = 4,529; PDI =2.65 430 94 211 105 20 1.22 0.7 M_(p) = 9,998; 17.1 0.0019 M_(w) =12,341; M_(n) = 4,993; PDI = 2.47 431 53 40 20 0 2.26 1.0 M_(p) = 1,562;31.8 0.01  0.9 IC M_(w) = 2,097; 0.1 EG M_(n) = 818; PDI = 2.56

[0405] TABLE 57 Ethylene/Acrylate Copolymerizations: Variation ofCatalyst Structure, Acrylate Structure and Temperature (0.004 mmol Cmpd,18 h, 100 equiv B(C₆F₅)₃, 50 equiv LiB(C₆F₅)₄, 9 mL p-Xylene, 6.9 MPa E)Acrylate Temp. Acrylate Yield Incorp Total Ex. Cmpd ° C. 1 mL G mol %M.W. Me 432 45 80 EGPEA 0.070 0.6 M_(p) = 24,391; M_(w) = 28,348; 8.50.5 IC M_(n) = 11,007; PDI = 2.58 0.1 EG 433 45 80 HA 0.294 1.0 M_(p) =45,116; M_(w) = 71,337; 14.2 M_(n) = 14,837; PDI = 4.81 434 94 80 EGPEA0.074 0.5 M_(p) = 9,723; M_(w) = 13,173; 8.0 M_(n) = 6,276; PDI = 2.10435 94 80 HA 0.362 0.8 M_(p) = 14,965; M_(w) = 15,692; 12.4 M_(n) =6,605; PDI = 2.38 436 90 80 HA 0.286 0.8 M_(p) = 17,982; M_(w) = 17,990;9.7 M_(n) = 6,559; PDI = 2.74 437 45 40 EGPEA 0  —    — — 438 91 40EGPEA 0  —    — — 439 94 40 EGPEA 0  —    — —

Examples 440-555

[0406] In these Examples sometimes alkylaluminum compounds are used ascocatalysts. These alkylaluminums were purchased from commercialsources, PMAO-IP (97) (polymethylaluminoxane from Akzo-Nobel, Inc., 12.7wt % aluminum in toluene, (0.88 g/ml at 30° C.)) or synthesized byliterature methods, (AlMe₂(Et₂O)₂) (MeB(C₆F₅)₃) (98) (WO0011006),AlMe(2,6-t-Bu-4-Me(OC6I₂))₂ (99) (A. P. Shreve, et al., Organometallics,vol. 7, p. 409 (1988)), and (Al-i-Bu₂(OC₆F₅))₂ (100) (D. G. Hendershot,et al., Organometallics, vol. 10 p. 1917 (1991)).

[0407] The transition metal complexes (101-117) are either isolatedcompounds or in situ generated from a combination of compounds. Suchcombinations are shown under the compound designation (number).Syntheses of compounds other than α-diimines or their complexes aredescribed in the following references:

[0408] 45-97, 101, 102, 103, 104, 105, 109, 110, 116 and 117, areα-diimines and/or Ni complexes the same as or similar to those describedin U.S. Pat. No. 6,034,259 and references therein, and U.S. Pat. No.6,103,658, and these α-diimines and/or Ni complexes are made by methodssimilar to those described therein. The synthesis of the ligand for 79is reported in Y. Yamamoto et al., J. Organometal. Chem., vol. 489, p.21-29 (1995), and K. Sugano, et al., Chem. Lett., vol. 1991 p. 921-924.

[0409] The synthesis of the α-diimine for 110 is described in U.S. Pat.No. 6,103,658.

[0410] Methods for making 115 are found in U.S. Pat. No. 6,174,975.

[0411] Synthesis of 108 is found in previously incorporated U.S. patentapplication ______ (filed concurrently on May 31, 2001, Applicant'sreference CL1655 US NA).

[0412] Syntheses of 106 and 107 are found herein. All of the immediatelydocuments are hereby included by reference.

[0413] Metal complexes or ingredients for in situ preparations are shownbelow:

General Polymerization Procedure for Examples 440-555.

[0414] In a drybox, a glass insert was loaded with a combination ofligand and metal precursor or an isolated metal precatalyst and 2 mL ofsolvent. The solution was cooled to −30° C. and a solid portion ofaluminum cocatalyst (such as 98, 99 or 100) or solution of PMAO-IP (97)was added followed by 4 mL of solvent and the solution was cooled to−30° C. This cooling was done to prevent any polymerization catalystdecomposition prior to contact with the monomers, in case the catalystwas thermally unstable. A solution was made with salt (see below),comonomer and 3 mL of solvent. The solution was added to the glassinsert and then cooled to −30° C. The insert was capped and placed intodouble ziplock bags. Outside the drybox the rack was transferred to apressure tube and flushed with ethylene. The pressure tube waspressurized with ethylene and heated to the desired temperature andmechanically shaken for the duration of time listed in the table. Thereaction solution was quenched with 30 mL of methanol or acidic methanol(10:90 HCl methanol solution) and the polymer was isolated byfiltration, rinsed with additional methanol and dried under vacuum.

[0415] Polymerization results are presented in Tables 58-64. A shortdescription/explanation for each table is given below. “Salt” in thesetables indicates the addition of NaBAF or LiB(C₆F₅)₄ to thepolymerization solution and it appeared to inhibit or prevent acrylatehomopolymerization, and will be shown as simply Na or Li in the table.

[0416] Table 58: Table 58 contains examples with Ni catalysts, diiminewith Ni(acac)₂, and alkylaluminum cocatalysts for EG-PEA and ethylenecopolymerization. At these high ratios of Ni to salt and Al cocatalystswe had some significant acrylate homopolymerization. The acrylatehomopolymer was found in two forms, a powder which was a mixture ofcopolymer with some acrylate homopolymer as identified by ¹H NMR, and agelatin consisting of acrylate homopolymer which was physicallyseparated and not included in the polymer weight in the tables. Thesolution volume was approximately 10 mL in each case, therefore, thesolvent added was 10 mL minus the volume added for the liquid comonomer.

[0417] Table 59: Table 59 shows examples of some of the better catalystsunder conditions with low concentration of Ni and high concentration ofsalt and Al cocatalysts. In these examples consistently good yields ofEGPEA/ethylene copolymer were obtained. Further characterization ofthese polymers is indicated by Mw from GPC as well as incorporation ofacrylate (mole %) in the copolymer that was calculated from ¹H NMRspectra of the polymer.

[0418] Table 60: This table has very low Ni concentrations and moreacrylate homopolymer and low yields of polymer are obtained overall.

[0419] Table 61: Different combinations of Ni compounds and cocatalystsare used.

[0420] Table 62: Examples for E-10-U copolymerizations with ethylene.

[0421] Table 63: Hexyl acrylate copolymerization with Ni catalyst.

[0422] Table 64: Other catalysts for EGPEA copolymerization. TABLE 58Ethylene and EGPA copolymerization (18 h, 6.9 MPa E, 0.02 mmol Ni) Cata-lyst Salt Yield Ex. mmol (eq) Al (eq) EGPEA solvent Temp (g) 440 104 Li(5) 100 (50) 1 mL 1,2,4-TCB 120° C. 1.439 441 104 Li (5) 100 (50) 2 mL1,2,4-TCB 120° C. 1.033 442 104 Na (5)  97 (200) 2 mL 1,2,4-TCB 120° C.6.011 443 104 Li (5) 100 (50) 2 mL p-xylene 120° C. 2.982 444 104 Li (5) 99 (50) 1 mL 1,2,4-TCB 120° C. 6.522 445 103 Li (5) 100 (50) 1 mLp-xylene 100° C. 1.287 446 103 Na (5)  97 (200) 1 mL p-xylene 100° C.5.077 447 104 Li (5) 100 (50) 1 mL p-xylene 100° C. 9.073 448 104 Na (5) 97 (200) 1 mL p-xylene 100° C. 3.96 449 104 Na (5) 100 (50) 1 mL1,2,4-TCB 100° C. 2.179 450 103 Li (5) 100 (50) 1 mL 1,2,4-TCB 100° C.3.053 451 103 Li (5)  97 (200) 1 mL 1,2,4-TCB 100° C. 5.977 452 104 Li(5)  97 (200) 1 mL 1,2,4-TCB 100° C. 6.114 453 105 Li (5)  97 (200) 1 mL1,2,4-TCB 100° C. 1.109 454 105 Li (5) 100 (50) 1 mL 1,2,4-TCB 100° C.3.392 455 116 Na (5) 100 (50) 1 mL 1,2,4-TCB 100° C. 1.931 456 103 Na(5) 100 (50) 1 mL 1,2,4-TCB 100° C. 1.269 457 103 Na (5)  97 (200) 1 mL1,2,4-TCB 100° C. 5.066 458 105 Na (5) 100 (50) 1 mL 1,2,4-TCB 100° C.4.628 459 104 Na (10) 100 (50) 1 mL 1,2,4-TCB 100° C. 0.387 460 104 Na(5)  97 (200) 1 mL 1,2,4-TCB 100° C. 6.538 461 104 Li (5) 100 (50) 1 mL1,2,4-TCB 100° C. 1.131 462 104 Li (5) 100 (50) 1 mL 1,2,4-TCB 100° C.4.477 463 104 no salt 100 (50) 1 mL 1,2,4-TCB 100° C. 1.198 464 104 Na(1) 100 (50) 1 mL 1,2,4-TCB 120° C. 0.50 465 104 Na (1) 100 (50) 1 mL1,2,4-TCB 120° C. 0.260 466 104 Na (1)  97 (200) 1 mL 1,2,4-TCB 120° C.5.411 467 104 Na (5) 100 (50) 1 mL 1,2,4-TCB 120° C. 0.176 468 104 Na(1) 100 (50) 1 mL 1,2,4-TCB 100° C. 0.254 469 104 Na (1)  97 (200) 1 mL1,2,4-TCB 100° C. 4.231 470 104 Na (5) 100 (50) 1 mL 1,2,4-TCB 100° C.1.460

[0423] TABLE 59 Ethylene and EGPEA Copolymerization (6.9 MPa E, p-xylenesolvent) Ex. Catalyst mmol Ni Salt eq Al eq mL acrylate Hrs Temp YieldKg/g Ni Mw Mol % Ac 471 101 0.002 Li (250) 98 (250) 1.0 18 120 4.766 4119051 0.36 472 101 0.002 Li (250) 98 (250) 1.5 18 120 3.170 27 168300.64 473 106 0.002 Li (250) 98 (250) 1.0 18 120 8.332 71  55390.17^(i)/0.19^(e) 474 101 0.001 Li (750) 98 (500) 1.0 18 120 2.576 4416000 0.57 475 101 0.004 Li (125) 98 (125) 1.0 18 100 7.24 31 27476 0.70476 101 0.002 Li (250) 98 (250) 1.0 18 100 4.749 40 25432 0.42 477 1010.002 Li (250) 98 (250) 1.5 18 100 3.213 27 22992 0.61 478 106 0.002 Li(250) 98 (250) 1.0 18 100 4.398 37  7262 0.19^(i)/0.16^(e) 479 101 0.001Li (750) 98 (500) 1.0 18 100 3.374 57 24042 0.30 480 101 0.004 Li (125)98 (125) 1.0 64 120 15.08 64 17153 0.29 481 101 0.002 Li (250) 98 (250)1.0 64 120 10.521 90 16817 0.47 482 101 0.002 Li (250) 98 (250) 1.5 64120 9.455 80 17930 0.8  483 106 0.002 Li (250) 98 (250) 1.0 64 120 7.83367  5469 0.20^(i)/0.18^(e) 484 107 0.002 Li (250) 98 (500) 1.0 64 1201.191 10  2045 ND 485 101 0.004 Li (125) 98 (125) 1.0 64 100 13.073 5626512 0.41 486 101 0.002 Li (250) 98 (250) 1.0 64 100 8.807 75 254721.2  487 101 0.002 Li (250) 98 (250) 1.5 64 100 6.183 53 23585 0.84 488106 0.002 Li (250) 98 (250) 1.0 64 100 7.100 60  6803 0.15^(i)/0.13^(e)489 107 0.002 Li (250) 98 (500) 1.0 64 100 0.834 7  3135 ND 490 1020.004 Li (125) 100 (250)  1.0 18 120 7.259 31 13945 0.25 491 102 0.004Li (125) 98 (125) 1.0 18 120 9.147 39 14056 0.35 492 102 0.004 Li (125)98 (125) 2.0 18 120 3.23 14 11652 0.94 493 101 0.004 Li (125) 100 (250) 1.0 18 120 6.165 26 13988 0.33 494 101 0.004 Li (125) 98 (125) 1.0 18120 9.355 40 15724 0.49 495 102 0.02 Li (10) 100 (25)  1.0 18 120 6.58 6N/A 0.55 496 102 0.02 Li (10) 98 (25)  1.0 18 120 18.921 16 N/A 0.34 497106 0.004 Li (25) 98 (50)  1.0 18 100 4.190 18 N/A 0.22^(i)/0.29^(e) 498108 0.004 Li (25) 98 (50)  1.0 18 100 0.123 0.5 N/A ND 499 107 0.004 Li(25) 98 (50)  1.0 18 100 2.114 9 N/A 0.38^(i)/0.37^(e) 500 101 0.004 Li(25) 98 (50)  1.0 18 100 2.750 12 N/A 0.42 501 102 0.004 Li (25) 98(50)  1.0 18 100 1.547 7 10621 0.48

[0424] TABLE 60 Ethylene and acrylate Copolymerization (18 h, 120° C.,6.9 MPa E, p-xylene solvent, Al compound 98) Ex. Catalyst mmol Ni Salteq Al eq mL acrylate Yield Kg/g Ni Mw Mol % Ac 502 101 0.001 Li (500) (500) 1.0 EGPEA 3.443 59 17680 copoly 503 101 0.0005 Li (1000) (1000)1.0 EGPEA 1.998 34 16178 copoly 504 106 0.001 Li (500)  (500) 1.0 EGPEA1.560 27  5500 copoly 505 106 0.0005 Li (1000) (1000) 1.0 EGPEA 1.08 37 5550 ND 506 109 0.001 Li (500)  (500) 1.0 EGPEA 0.576 10 17704 ND 507101 0.001 Li (500)  (500) 0.5 MA 3.024 52 15041 Copoly 508 101 0.0005 Li(1000) (1000) 0.5 MA 1.507 51 N/A N/A 509 106 0.001 Li (500)  (500) 0.5MA 0.225 4 N/A N/A 510 106 0.0005 Li (1000) (1000) 0.5 MA 0.390 13 N/AN/A 511 109 0.001 Li (500)  (500) 0.5 MA 0.553 9 N/A N/A 512 101 0.001Li (500)  (500) 0.5 HA 1.08 18 N/A N/A 513 101 0.0005 Li (1000) (1000)0.5 HA 0.982 33 N/A N/A 514 106 0.001 Li (500)  (500) 0.5 HA 0.314 5 N/AN/A 515 106 0.0005 Li (1000) (1000) 0.5 HA 0.303 10 N/A N/A 516 1090.001 Li (1000) (1000) 0.5 HA 0.672 11 N/A N/A

[0425] TABLE 61 Ethylene and EGPEA Copolymerization (18 h, 120° C., 6.9MPa E, p-xylene solvent, 1.0 ml EGPEA) Ex. Catalyst Mmol Ni Salt eq Aleq Yield Mw 517 104 0.004 Li (125) 98 (125) 8.451 17004 518 117 0.004 Li(125) 98 (125) 0.543 17988, 26687 519 106 0.002 Li (250) 98 (250) 2.6444787 520 115 0.01 Li (30)  99 (20)/B(C₆F₅)₃ (10) 0.307 N/A 521 110 0.01Li (30)  99 (20)/B(C₆F₅)₃ (10) 1.417 26934 522 102 0.01 Li (30)  99(20)/B(C₆F₅)₃ (10) 8.456 14038 523 101 0.01 Li (30)  99 (20)/B(C₆F₅)₃(10) 8.283 13607 524 111 0.01 Li (30)  100 (50) 0.897 N/A 525 101 0.01Li (30)  98 (25) 11.741 11838 526 101 0.01 Li (30)  99 (25) 2.647 11370527 102 0.01 Li (30)  99 (25) 2.412 11766 528 106 0.002 Li (150) 98(250) 1.612 4235 529 106 0.002 Li (150) 100 (500) 1.559 3812, 6321 530106 0.002 Li (150) 99 (500) 0.450 N/A 531 107 0.002 Li (150) 98 (250)0.929 N/A 532 107 0.002 Li (150) 100 (500) 1.595 1785 533 107 0.002 Li(150) 99 (500) 0.782 N/A 534 108 0.002 Li (150) 98 (250) 0.263 N/A 535108 0.002 Li (150) 100 (500) 0.839 N/A 536 108 0.002 Li (150) 99 (500)0.387 N/A

[0426] TABLE 62 Ethylene and E-10-U Copolymerization (18 h, p-xylenesolvent mL- Cata- mmol E- T Pres. Ex. lyst Ni Salt eq Al eq 10-U ° C.MPa Yield Mw 537 102 0.01 0 98 2.0 60 1.0 2.50 N/A  (50) 538 106 0.002Li (150) 98 1.0 120  6.9 8.525 6043 (250) 539 106 0.004 Li (75) 98 1.7120  6.9 0.531 4820 (125) 540 115 0.01 Li (30) 99 1.7 120  6.9 0.101 N/A (50) 541 106 0.004 Li (75) 98 1.7 60 3.5 0.018 N/A (125) 542 115 0.01Li (30) 99 1.7 60 3.5 0.091 N/A  (50) 543 111 0.02 Na (1) 100  1.1 805.2 9.770 N/A  (50) 544 112 0.02 Na (1) 100  1.1 80 5.2 0.160 N/A  (50)

[0427] TABLE 63 Copolymerization of ethylene and HA (18 h, 100° C., 6.9MPa E) mL Cata- mmol acryl- Ex. lyst Ni Salt eq Al eq ate solvent YieldMw 545 104 0.02 Na (5) 97 1.0 1,2,4TCB 4.881  4177 (200) HA 546 104 0.02Na (5) 97 2.0 1,2,4TCB 3.392 21281 (200) HA 547 104 0.02 Li (5) 99 1.01,2,4TCB 6.443 21943  (50) HA 548 104 0.02 Li (5) 99 1.0 p-xylene 7.65529495  (50) HA

[0428] TABLE 64 Copolymerization of Ethylene and EGPEA (18 h, 120° C.,6.9 MPa E, 0.01 mmol Ni) mL Cata- acryl- Ex. lyst Salt eq Al eq atesolvent Yield Mw 549 103 Li (50) 98 (50) 1.0 p-xylene 19.010 13399 550116 Li (50) 98 (50) 1.0 p-xylene 16.671 15559 551 102 Li (50) 98 (50)1.0 p-xylene 11.724 12804 552 102 Na (50) 97 (100) 1.0 1,2,4-TCB 5.84826061 553 102 Na (50) 97 (50) 1.0 1,2,4-TCB 5.550 11620 554 103 Na (50)97 (100) 1.0 1,2,4-TCB 10.108 12359 555 103 Na (50) 97 (50) 1.01,2,4-TCB 9.116 14836

Examples 556-651

[0429] Various isocyanates were used with a single precursor,di-t-butylphosphinomethyl lithium to prepare variously substitutedligands (see below). Nickel complexes were then prepared in situ, andpolymerizations carried out.

[0430] All reactions were performed under an atmosphere of nitrogen. Theisocyanates for the catalyst preparation were obtained from commercialsources, and were purified by distillation, sublimation, orrecrystallization; the compounds were stored under nitrogen before use.TCB was purchased anhydrous and used as is. Additional solvents weredistilled from drying agents under nitrogen using standard procedures:chlorobenzene from P₂O₅; and THF, from sodium benzophenone ketyl, Ni(II)allyl chloride and NaBAF were prepared according to the literature.

[0431] Ninety-five isocyanates were prepared as THF solutions (0.0500 M)and are listed in Table 65. These solutions were prepared in glass vialscapped with Teflon® lined silicone septa to maintain an inert atmosphereand prevent evaporation.

[0432] Preparation of catalyst solutions was performed according toequation 1.

[0433] In a typical procedure, each sample was prepared by addingsequentially 150(±3) μL of an isocyanate solution (0.0500 M in THF)followed by 150(±3) μL of a solution of (t-Bu)₂PCH₂Li (0.0500 M in THF),followed by 150(±3) μL of a solution of (NiCl(η³—C₃H₅))₂ (0.0250 M inTHF) to a septa sealed 2 mL glass vial. The solvent was then removedfrom each vial by purging with a nitrogen gas stream and each vial wasthen dried for 2 h in a vacuum chamber. A solution of cocatalyst(B(C6F₅)₃, B(C₆H₅)₃ or NaBAF) 300 μL (0.1250 M in chlorobenzene or TCB)was added into each vial. Each vial was placed in a high-pressurereactor. The reactor was pressurized to the desired pressure (typically6.9 MPa or 1.0 MPa) with ethylene and kept at that pressure for 18 h. Atthe end of the run, the solvent was removed from each vial under vacuum.After this operation each vial was weighed to obtain a polymer yield. Torapidly determine the presence of copolymer, a sample was taken out ofeach vial and placed in an NMR tube, CDCl₃ was added and the solutionwas analyzed submitted by ¹H NMR spectroscopy. In some (usuallypromising) cases, samples were dissolved in TCE and submitted for hightemperature ¹³C NMR spectroscopy.

[0434] Condition 1

[0435] Run at room temperature and 6.9 MPa of ethylene. Five equivalentsof tris(pentafluorophenyl)borane were present as a cocatalyst. Eighteenhours was chosen as the run time to allow for comparison of the lowestand highest yielding catalysts. Results are presented in Table 65. Theexperimental procedure was repeated several times and despite somechanges in yields, activity trends remained the same.

[0436] Condition 2

[0437] This was the same as Condition 1, except the ethylene pressurewas 1.0 MPa. Results are shown in Table 65.

[0438] Condition 3

[0439] This was the same as Condition 1, except 5 equivalents oftriphenylborane was used as a cocatalyst and the polymerization was runat 1.0 MPa ethylene pressure. This condition was repeated several timeswith similar results each time. Results are shown in Table 65.

[0440] Condition 4

[0441] This was run under the same conditions as Condition 1 except, oneequivalent of NaBAF was added (150 μl of a 0.05M solution in THF) afterthe addition of nickel allyl chloride.

[0442] Condition 5

[0443] Run at room temperature and under 6.9 MPa of ethylene. Fiveequivalents of tri(pentafluorophenyl)borane were used. The cocatalyst,instead of being dissolved in pure TCB was dissolved in a 1:5 (v:v)mixture of EGPEA and TCB. Because EGPEA has a high boiling point, vialswere weighed out immediately after the polymerization reaction withoutdrying. Relative yields were obtained by difference of the weights ofthe “wet” vials and the pre-tared vials. Results are presented in Table65. This condition was repeated several times and despite some changesin yields, activity trends remain the same.

[0444] Condition 6

[0445] This was the same as Condition 5 except the polymerization wasrun at 100° C. Results are presented in Table 65. This condition wasrepeated several times and despite some changes in yields, activitytrends remain the same.

[0446] Condition 7

[0447] This was run in the same manner as Condition 6 except 1equivalent of NaBAF added (150 μl of a 0.05M solution in THF) was alsoadded after the nickel allyl chloride was added. Results are given inTable 65. ¹³C NMR analysis indicates that the polymer in Example 582gives a copolymer with 1.04 mole incorporation under this condition.

[0448] Condition 8

[0449] This condition was the same as Condition 7, except the EGPEAcontained 250 ppm of benzoquinone as a free radical polymerizationinhibitor. Results are given in Table 65. ¹³C NMR analysis indicatesthat the polymers produced in Examples 583 and 591 gave copolymers withtrace incorporation of EGPEA, the polymer of Example 585 had 0.17 mol %incorporation of EGPEA, the polymer of Example 632 had 0.51 mol %incorporation of EGPEA, and the polymer of Example 640 had 0.90 mol %incorporation of EGPEA, all under this condition. TABLE 65 CONDITION Ex.NAME 1 2 3 4 5 6 7 8 556 TRANS-2-PHENYLCYCLOPROPYL ISOCYANATE 1.22620.3589 0.0875 0.1950 0.4978 0.4518 0.249 0.3437 557 PHENYL ISOCYANATE0.6409 0.1067 0.046 0.0982 0.4686 0.6287 0.3906 0.3762 558 2-BROMOPHENYLISOCYANATE 0.5133 0.1321 0.0485 0.0994 0.4733 0.7043 0.3068 0.3811 5592-FLUOROPHENYL ISOCYANATE 0.3426 0.1074 0.0703 0.1568 0.437 0.54790.4299 0.4407 560 2,4-DIFLUOROPHENYL ISOCYANATE 0.5988 0.1008 0.06150.1875 0.4797 0.7257 0.448 0.4373 561 2,6-DIFLUOROPHENYL ISOCYANATE0.3429 0.1111 0.0392 0.0974 0.4859 0.6638 0.4485 0.4626 5622-CHLOROPHENYL ISOCYANATE 0.4882 0.1215 0.0462 0.1257 0.5097 0.69950.4705 0.4645 563 2,3-DICHLOROPHENYL ISOCYANATE 0.4516 0.1075 0.04340.1196 0.413 0.7917 0.4686 0.4702 564 2,6-DICHLOROPHENYL ISOCYANATE0.4058 0.1061 0.0506 0.1088 0.4688 0.7486 0.4394 0.3883 5652-METHOXYPHENYL ISOCYANATE 1.0975 0.113 0.0584 0.1183 0.4762 0.59930.5925 0.4257 566 2,4-DIMETHOXYPHENYL ISOCYANATE 1.0943 0.1198 0.04150.1243 0.5168 0.6874 0.561 0.3869 567 2-ETHOXYPHENYL ISOCYANATE 1.14730.1133 0.044 0.1469 0.4535 0.7136 0.4882 0.4019 5682-(TRIFLUOROMETHYL)PHENYL ISOCYANATE 0.4246 0.1013 0.0424 0.2715 0.51810.7255 0.4381 0.4564 569 O-TOLYL ISOCYANATE 0.6267 0.1229 0.0862 0.17570.4151 0.7253 0.5005 0.4611 570 2,6-DIMETHYLPHENYL ISOCYANATE 0.54540.1198 0.0603 0.1429 0.4016 0.6963 0.4101 0.3991 571 2-ETHYLPHENYLISOCYANATE 0.6052 0.1166 0.0781 0.1382 0.4254 0.6031 0.4255 0.4705 5723-BROMOPHENYL ISOCYANATE 0.587 0.1001 0.0761 0.1376 0.4664 0.6937 0.32570.4718 573 3,4-DICHLOROPHENYL ISOCYANATE 0.813 0.0945 0.0536 0.17960.4698 0.7749 0.5005 0.5852 574 4-BROMOPHENYL ISOCYANATE 0.6361 0.10740.0577 0.1428 0.4594 0.7041 0.5411 0.4898 575 4-FLUOROPHENYL ISOCYANATE0.8563 0.1152 0.0986 0.1222 0.4424 0.6754 0.5557 0.3903 5764-CHLOROPHENYL ISOCYANATE 0.7498 0.1242 0.0641 0.1239 0.4887 0.33190.4404 0.4185 577 4-METHOXYPHENYL ISOCYANATE 0.5989 0.1302 0.0778 0.12450.4746 0.7178 0.6034 0.5034 578 4-(TRIFLUOROMETHYL)PHENYL ISOCYANATE0.651 0.0773 0.0539 0.1410 0.469 0.7685 0.4609 0.4037 579 P-TOLYLISOCYANATE 0.7736 0.1045 0.0744 0.1335 0.4849 0.6127 0.2255 0.5482 580TERT-BUTYL ISOCYANATE 1.0498 0.0808 0.1742 0.3829 0.422 1.3345 0.69140.6516 581 (S)-(−)-1-PHENYLETHYL ISOCYANATE 0.873 0.1171 0.0923 0.12760.4037 0.8667 0.6858 0.6728 582 ISOPROPYL ISOCYANATE 0.2012 0.07770.0107 0.1421 0.2749 0.6658 0.394 0.5266 583 ETHYL ISOCYANATE 1.33470.1538 0.0805 0.1814 0.4434 1.2218 0.5436 0.6256 584 ALLYL ISOCYANATE0.9033 0.1644 0.0976 0.1347 0.6952 1.0612 0.4884 0.6627 585 N-BUTYLISOCYANATE 1.1664 0.1843 0.0637 0.1220 0.4643 1.8471 0.4761 0.6228 586CYCLOHEXYL ISOCYANATE 0.8991 0.0932 0.1353 0.2726 0.488 1.791 0.65140.6029 587 1-NAPHTHYL ISOCYANATE 0.7214 0.0943 0.1161 0.1352 0.43440.7355 0.3902 0.4148 588 2,6-DIISOPROPYLPHENYL ISOCYANATE 0.4853 0.12040.0914 0.1423 0.3988 0.6511 0.329 0.077 589 BENZYL ISOCYANATE 1.14790.1492 0.1403 0.2398 0.5289 0.7776 0.5322 0.62 5903,5-BIS(TRIFLUOROMETHYL)PHENYL ISOCYANATE 0.7095 0.1125 0.1214 0.12710.4763 0.8135 0.4492 0.4084 591 2,5-DIFLUOROPHENYL ISOCYANATE 0.41580.1146 0.0131 0.1836 0.4606 0.4177 0.3512 0.4228 5922,4,5-TRICHLOROPHENYL ISOCYANATE 0.3766 0.1572 0.0236 0.2077 0.48210.8006 0.4808 0.5625 593 2,4,6-TRICHLOROPHENYL ISOCYANATE 0.5539 0.10110.0304 0.1775 0.4748 0.7127 0.4425 0.4596 594 2-ISOPROPYLPHENYLISOCYANATE 0.6127 0.1362 0.0693 0.1165 0.4707 0.6892 0.4572 0.4482 5952,3-DIMETHYLPHENYL ISOCYANATE 0.8057 0.1345 0.0872 0.1027 0.4844 0.72510.4875 0.4715 596 4-METHOXY-2-METHYLPHENYL ISOCYANATE 0.6799 0.16680.0762 0.1207 0.4756 0.7112 0.3862 0.6706 5975-CHLORO-2,4-DIMETHOXYPHENYL ISOCYANATE 0.7214 0.1385 0.0716 0.10910.4337 0.7176 0.4579 0.6935 598 3,5-DICHLOROPHENYL ISOCYANATE 0.66040.106 0.0931 0.1802 0.4473 0.7304 0.4414 0.6873 5995-CHLORO-2-METHOXYPHENYL ISOCYANATE 0.5286 0.113 0.057 0.1062 0.46210.7468 0.4694 0.4146 600 3,4,5-TRIMETHOXYPHENYL ISOCYANATE 0.636 0.12750.0592 0.1148 0.4942 0.7509 0.523 0.7049 601 3,5-DIMETHOXYPHENYLISOCYANATE 0.6032 0.1015 0.0839 0.1171 0.4479 0.7324 0.5068 0.6608 6023-(METHYLTHIO)PHENYL ISOCYANATE 0.7208 0.0708 0.0715 0.0954 0.46260.7488 0.4867 0.3239 603 3,5-DIMETHYLPHENYL ISOCYANATE 0.7576 0.10960.088 0.1073 0.4382 0.6381 0.4942 0.5342 604 2-METHOXY-5-METHYLPHENYLISOCYANATE 0.721 0.0987 0.0217 0.1216 0.4154 0.6463 0.4118 0.3875 6054-IODOPHENYL ISOCYANATE 0.5297 0.0883 0.0413 0.0881 0.4478 0.6757 0.16960.4612 606 4-PHENOXYPHENYL ISOCYANATE 0.5906 0.1005 0.0936 0.0609 0.44850.6619 0.4136 0.4024 607 4-(METHYLTHIO)PHENYL ISOCYANATE 0.4779 0.09370.1195 0.1086 0.4006 0.737 0.4584 0.5003 608 4-ISOPROPYLPHENYLISOCYANATE 0.5101 0.0769 0.0509 0.2092 0.4664 0.6183 0.407 0.4313 609OCTYL ISOCYANATE 0.9398 0.2845 0.1001 0.1300 0.486 1.4104 0.4526 0.4872610 2,4,6-TRIMETHYLPHENYL ISOCYANATE 0.7957 0.1156 0.067 0.1761 0.39830.6478 0.2829 0.2392 611 2-ISOPROPYL-6-METHYLPHENYL ISOCYANATE 0.66180.1211 0.0738 0.0693 0.3989 0.577 0.3896 0.186 612 2,6-DIETHYLPHENYLISOCYANATE 0.5731 0.1098 0.0834 0.1372 0.4013 0.5009 0.4077 0.3754 6134-(TRIFLUOROMETHOXY)PHENYL ISOCYANATE 0.3959 0.0939 0.094 0.1096 0.46920.7275 0.454 0.4577 614 4-(TRIFLUOROMETHYLTHIO)PHENYL ISOCYANATE 0.59440.1932 0.0353 0.0783 0.4089 0.7622 0.4608 0.4214 6152-CHLORO-5-(TRIFLUOROMETHYL)PHENYL ISOCYANATE 0.7326 0.105 0.0647 0.08760.4005 0.7298 0.2464 0.4005 616 2-CHLORO-6-METHYLPHENYL ISOCYANATE0.5883 0.1192 0.0613 0.1059 0.486 0.7034 0.3467 0.0977 6172,4,5-TRIMETHYLPHENYL ISOCYANATE 0.5944 0.1185 0.0966 0.1776 0.44170.6765 0.6212 0.4493 618 2-TERT-BUTYL-6-METHYLPHENYL ISOCYANATE 0.81710.1604 0.0643 0.0848 0.4026 0.4572 0.1104 0.1466 6193-CHLORO-2-METHOXYPHENYL ISOCYANATE 0.5302 0.1404 0.0814 0.1427 0.4590.782 0.4478 0.4052 620 3-CHLORO-4-FLUOROPHENYL ISOCYANATE 0.4591 0.09450.1072 0.1099 0.4595 0.7624 0.4699 0.4507 621 4-BROMO-2,6-DIMETHYLPHENYLISOCYANATE 0.5464 0.13 0.1132 0.1166 0.4638 0.6462 0.4518 0.4093 6222,6-DIBROMO-4-FLUOROPHENYL ISOCYANATE 0.391 0.1774 0.0342 0.1319 0.4010.7821 0.4095 0.4055 623 PHENETHYL ISOCYANATE 0.8483 0.2427 0.11980.1491 0.4586 1.256 0.4523 0.4349 624 2,4-DICHLOROBENZYL ISOCYANATE0.8151 0.1546 0.1385 0.1366 0.5296 0.7782 0.5995 0.7227 6252-(METHYLTHIO)PHENYL ISOCYANATE 0.5143 0.0504 0.0428 0.2408 0.41570.7048 0.4431 0.2206 626 2-BIPHENYLYL ISOCYANATE 0.5349 0.0985 0.05530.0910 0.4516 0.6602 0.2644 0.3317 627 3-IODOPHENYL ISOCYANATE 0.65150.1149 0.0254 0.1153 0.4593 0.6019 0.4004 0.4163 628 4-BIPHENYLYLISOCYANATE 0.6505 0.1266 0.0859 0.1763 0.4478 0.6759 0.5337 0.6352 6291-(4-BROMOPHENYL)ETHYL ISOCYANATE 0.6759 0.1045 0.1104 0.1413 0.39930.8374 0.5492 0.639 630 3-ISOCYANATOPROPYLTRIETHOXYSILANE 0.781 0.14470.0601 0.1449 0.4447 0.7711 0.68 0.63 6312,6-DICHLOROPYRID-4-YLISOCYANATE 0.3357 0.0929 0.0374 0.2234 0.4640.4699 0.4956 0.4817 632 2-BROMO-4,6-DIFLUOROPHENYL ISOCYANATE 0.38530.3034 0.0332 0.1377 0.4981 0.7634 0.3552 0.4703 633(R)-(+)-1-PHENYLETHYL ISOCYANATE 1.1374 0.0968 0.1314 0.1229 0.39980.7987 0.6867 0.6773 634 1-(1-NAPHTHYL)ETHYL ISOCYANATE 0.6728 0.0960.1357 0.0961 0.3994 0.776 0.6416 0.6752 635 3,4-DIFLUOROPHENYLISOCYANATE 0.5316 0.0918 0.1369 0.1027 0.3697 0.6019 0.3812 0.3829 6363-ISOPROPENYL-ALPHA,ALPHA-DIMETHYLBENZYL ISO- 0.8534 0.0668 0.12060.1723 0.3914 0.807 0.5119 0.5786 CYANATE 637 2-(TRIFLUOROMETHOXY)PHENYLISOCYANATE 0.4523 0.1001 0.1084 0.1736 0.4919 0.7178 0.3949 0.3472 6381-ADAMANTYL ISOCYANATE 1.1437 0.1182 0.1838 0.3750 0.5557 1.0394 0.66030.6336 639 1,1,3,3-TETRAMETHYLBUTYL ISOCYANATE 1.109 0.1097 0.08030.1382 0.387 1.0645 0.6671 0.6077 640 4-BROMO-2-FLUOROPHENYL ISOCYANATE0.3947 0.1083 0.0481 0.1094 0.4643 0.763 0.4426 0.5667 6412-FLUORO-5-METHYLPHENYL ISOCYANATE 0.4424 0.1073 0.0694 0.1698 0.47760.7708 0.4446 0.5312 642 2,3,4-TRIFLUOROPHENYL ISOCYANATE 0.9257 0.1630.0954 0.1493 0.4571 0.7804 0.4449 0.5111 643 4-(DIMETHYLAMINO)PHENYLISOCYANATE 0.5244 0.1365 0.0726 0.1531 0.4774 0.7787 0.6345 0.6669 6442-(DIFLUOROMETHOXY)PHENYL ISOCYANATE 0.6934 0.1497 0.0594 0.2253 0.46780.7701 0.532 0.3925 645 4-(DIFLUOROMETHOXY)PHENYL ISOCYANATE 0.76210.1233 0.0703 0.1651 0.4521 0.7201 0.558 0.6245 646 2-CHLOROBENZYLISOCYANATE 0.8213 0.2136 0.1897 0.1704 0.6774 1.0548 0.5373 0.7148 6474-FLUOROBENZYL ISOCYANATE 0.9973 0.2161 0.1757 0.1925 0.5137 0.78970.4974 0.6074 648 4-METHOXYBENZYL ISOCYANATE 0.7301 0.2021 0.1636 0.22160.4744 0.8084 0.5537 0.719 6494-FLUORO-2-(TRIFLUOROMETHYL)PHENYL-ISOCYANATE 0.4066 0.0944 0.07170.1451 0.5543 0.7581 0.1094 0.5099 650 2,6-DIBROMO-4-ISOPROPYLPHENYLISOCYANATE 0.3894 0.125 0.0461 0.1033 0.4346 0.7307 0.1975 0.4574 6513-PYRIDYL ISOCYANATE 0.3692 0.1585 0.066 0.3655 0.491 0.6084 0.20170.069

Example 652 Synthesis of Catalyst Derived From t-Butyl Isocyanate

[0450] A 500-mL round-bottomed flask was charged with 536 mg (5.40 mmol)of t-butylisocyanate dissolved in ca. 30 mL THF. Then (t-Bu)₂P—CH₂Li(898 mg, 5.40 mmol) dissolved in ca. 30 mL THF was added. The reactionwas stirred for one h after which time, a solution of (Ni(C₃H₅)Cl)₂ (730mg, 2.70 mmol) in THF (ca. 30 mL) was added and stirred for anadditional one h and the solvent removed. The residue was washed withhexane and dried in vacuo to yield 1.80 g (83%) of a purple powder.¹H-NMR (CD₂Cl₂, 23° C., 300 MHz) : d 6.0-4.0 (broad signals), 4.0-2.0(broad signals), 1.0-0.0 (broad signals, t-Bu), ³¹P-NMR (CD₂Cl₂, 23° C.,300 MHz): δ 46.7 (s)

Examples 653-673

[0451] Toluene was purified according to R. H. Grubbs et. al.,Organometallics, 1996, 15, p. 1518-1520. Methyl acrylate was spargedwith nitrogen and passed through a column of activated neutral aluminain the drybox before use. In a drybox 1.77 g NaBAF, B(C₆F₅)₃ (see Table66), methyl acrylate (see Table 66) and all but 20 mL of the toluenewere combined. The total volume of the reaction mixture was 100 mL andthe amount of methyl acrylate and toluene were calculated on this basis.This solution was transferred to a metal addition cylinder in thedrybox, and the solution was then charged to a nitrogen-purged 450 mLjacketed autoclave. In the drybox 45 (0.0286 g) was dissolved in theremaining 20 mL of toluene and mixed for 30 minutes on a labVibramixer®. This solution was transferred via cannula under positivenitrogen pressure to a small metal addition cylinder attached to theautoclave. While stirring, the autoclave was charged with ethylene to350 kPa and vented three times. The reactor and its contents were heatedto the reaction temperature (Table 66) using a steam/water mixture inthe autoclave jacket. After achieving the desired operating temperature,the autoclave was pressurized with ethylene to 350 to 690 kPa below thedesired operating pressure (Table 66). The catalyst addition cylinderwas charged with ethylene to the desired operating pressure, and thecatalyst solution was then pressure injected to begin thepolymerization. Ethylene was fed to maintain a constant pressure. After6 h, the reaction was cooled to RT. All volatiles were removed from thereaction solution using a rotary evaporator. The evaporated residue waswashed with three 50-100 mL portions of methanol with decanting of themethanol into a fritted glass filter after each wash. The methanolinsoluble solids were then transferred to the filter with methanol andwashed on the filter with additional methanol. The solids were dried for18 hours at 60° C. in a vacuum oven. Molecular weights of the isolatedpolymer samples were determined by GPC. ¹³C NMR of the dried polymerswas used to calculate the weight % of homopoly(methyl acrylate), themole % MA content of the ethylene/methyl acrylate copolymer, and theamount of branching in the polymer. (See FIG. 3 for ¹³C peak assignmentsand formulas for the mole % calculations.) Weight % calculations weredone using the mole % values and the molecular weights of thecomponents. TABLE 66 Temp E Press. Methyl Ac- B (C₆F₅)₃ Isolated Wt %Homo- Mole % MA in Branching Ex. (° C.) (MPa) rylate (vol %) (moleequiv/Ni) Yield (g) poly MA copolymer CH₃/1000 CH₂ Mw Mw/Mn 653 100 4.120.0 200 0.7 65.65 1.60 32.3 2353 1.96 654 140 6.9 5.0 100 13.5 3.260.68 88.1 6273 2.11 655 100 6.9 5.0 200 3.67 0.01 0.57 33.0 17478 2.02656 140 6.9 5.0 300 24.96 2.22 0.31 86.7 6031 2.00 657 100 6.9 20.0 3000.72 14.46 1.17 59.2 4427 1.98 658 100 6.9 20.0 100 1.94 69.63 1.89 52.96494 2.33 659 140 6.9 20.0 200 7.3 48.59 1.41 86.9 3896 2.53 660 140 6.95.0 100 13.67 5.60 0.58 94.6 5850 2.15 661 100 6.9 20.0 100 1.85 74.441.96 37.1 5678 2.42 662 100 4.1 5.0 100 1.16 2.14 0.92 47.3 13332 1.97663 100 4.1 5.0 300 1.59 2.13 1.04 46.2 11085 2.07 664 120 5.5 12.5 1006.05 22.72 1.69 56.0 5888 1.95 665 120 4.1 5.0 200 7.59 2.71 0.88 68.87429 2.03 666 100 5.5 5.0 200 2.74 1.53 0.76 37.3 13347 2.02 667 140 4.15.0 200 14.44 6.91 1.00 99.2 4192 2.36 668 140 4.1 20.0 300 4.86 54.013.20 97.4 2298 1.99 669 140 4.1 20.0 100 4.0 74.77 1.15 121.5 2144 2.17670 100 4.1 5.0 100 1.47 7.61 1.24 45.2 11389 2.57 671 100 4.1 5.0 3002.58 1.82 0.64 42.1 8923 2.25 672 100 4.1 12.5 200 0.71 13.88 1.93 43.24858 1.82 673 140 4.1 20.0 100 4.6 75.97 2.60 110.5 2200 3.07

Examples 674-769

[0452] All reactions were performed under a nitrogen atmosphere. Theadditives were obtained from commercial sources and used as received.Solvents were purchased anhydrous and distilled from P₂O₅(chlorobenzene), sodium benzophenone ketyl (THF), CaH₂ (acetonitrile) orused as received (TCB, methanol).

[0453] The additives were prepared as solutions (0.0375 M) in THF (Ex.674-722), acetonitrile (Ex. 723-739), methanol (Ex. 740-754) and water(Ex. 755-758). These solutions were prepared in glass vials capped withTeflon® lined silicone septa to maintain inert atmosphere and preventevaporation.

[0454] The nickel compounds used are shown below.

[0455] General Polymerization Procedure: In a nitrogen flushed box, a150 μL or 750 μL of additive solution (0.0375 M) was added to a septumsealed 2 mL glass vial. The septum cap was removed and the solvent wasremoved under a nitrogen gas stream and the sample was dried for 20 miin a vacuum chamber. Additives for Ex. 763-773 were added to separate 2mL glass vials by weighing solid (0.0056 mmol or 0.028 mmol) directlyinto the vial. The vial was recapped and a solution (3 mL of THF) ofcatalyst A, B or C was added to the vial. Catalysts B and C may contain0-2 equiv of LiCl and we have assumed 1 equiv for the purposes ofcalculating a molecular weight. The septum cap was removed and thesolvent was removed under a nitrogen gas stream and the sample was driedfor 20 min in a vacuum chamber. The vial was recapped with a septum cap.A 0.300 mL polymerization solution containing solvent, cocatalyst(s) andacrylate monomer, if any, was added into each vial. Each vial was placedinto a high-pressure reactor and pressurized with ethylene to thedesired pressure and temperature for a total of 18 h. For ethylenepolymerization experiments the volatiles were removed from each vial ina heated (approx. 50° C.) vacuum chamber. The weight of the vial wasmeasured and the tare weight of the vial was subtracted to calculate theweight of polymer generated (catalyst residue is not taken intoconsideration). For ethylene copolymerization experiments the vial isweighed directly and the tare weight of the vial was subtracted tocalculate the relative weight of polymer generated (the solvent, monomerand catalyst residue are not subtracted from this weight). The amountsof polymers produced (in g) are given in Table 67. Polymerizationconditions are given below.

[0456] Condition 1: Catalyst B with 5 equiv of additive and 0.300 mL ofchlorobenzene. The polymerization was conducted at 6.9 MPa of ethyleneat RT for 18 h.

[0457] Condition 2: Catalyst B with 1 equiv of additive, 5 equiv ofB(C₆F₅)₃ and 0.300 mL of chlorobenzene. The polymerization was conductedat 1.0 MPa of ethylene at RT for 18 h.

[0458] Condition 3: Catalyst B with 5 equiv of additive, 1 equiv ofNaBAF and 0.300 mL of chlorobenzene solution (the chlorobenzene solutioncontained 2.5 volume % of diethyl ether). The polymerization wasconducted at 6.9 MPa ethylene at RT for 18 h.

[0459] Condition 4: Catalyst A with 1 equiv of additive, 5 equiv ofB(C₆F₅)₃, 5 equiv of LiB(C₆F₅)₄ and 0.300 mL of TCB solution (the TCBsolution contained 20 volume % of EGPEA). The polymerization wasconducted at 6.9 MPa of ethylene at 100° C. for 18 h.

[0460] Condition 5: Catalyst B with 1 equiv of additive, 5 equiv ofB(C₆F₅)₃, 5 equiv of LiB(C₆F₅)₄ and 0.300 mL of 1,2,4-TCB solution (the1,2,4-TCB solution contained 20 volume % of EGPEA). The polymerizationwas conducted at 6.9 MPa of ethylene at 100° C. for 18 h.

[0461] Condition 6: Catalyst A with 5 equiv of additive, 5 equiv ofLiB(C₆F₅)₄ and 0.300 mL of TCB solution (the TCB solution contained 20volume % of EGPEA). The polymerization was conducted at 6.9 MPa ofethylene at 100° C. for 18 h.

[0462] Condition 7: Catalyst C with 1 equiv of additive, 5 equiv ofB(C₆F₅)₃ and 0.300 mL of chlorobenzene. The polymerization was conductedat 3.5 MPa of ethylene at RT for 18 h. TABLE 67 CONDITION Ex. ADDITIVE 12 3 4 5 6 7 674 4-CHLOROPHENYLBORONIC ACID 0.090 0.568 0.123 0.635 0.7070.428 0.125 675 ALUMINUM CHLORIDE 0.296 0.076 0.138 0.472 0.405 0.1000.261 676 ALUMINUM ISOPROPOXIDE 0.009 0.188 1.000 0.668 0.597 0.4300.177 677 ALUMINUM PHENOXIDE 0.020 0.706 0.482 0.614 0.694 0.412 0.175678 ALUMINUM TRIS(2,2,6,6-TETRAMENTYL-3,5-HEPTANEDIONATE) 0.105 0.0670.059 0.572 0.612 0.422 0.133 679 ALUMINUM TRI-SEC-BUTOXIDE 0.028 0.1690.348 0.691 0.691 0.439 0.162 680 BORON TRIFLUORIDE TERT-BUTYL METHYLETHERATE 0.187 0.814 0.256 0.684 0.736 0.414 0.312 681 COPPER(I) ACETATE0.004 0.402 0.011 0.680 0.749 0.409 0.150 682 COPPER(I) BROMIDE 0.0050.426 0.032 0.671 0.667 0.423 0.134 683 COPPER(II) ACETATE 0.009 0.2960.013 0.685 0.681 0.429 0.073 684 COPPER(II) BROMIDE 0.005 0.174 0.0120.602 0.456 0.390 0.123 685 COPPER(II) CHLORIDE 0.004 0.218 0.072 0.6030.137 0.449 0.146 686 COPPER(II) TRIFLUOROMETHANESULFONATE 0.057 0.0520.042 0.618 0.789 0.460 0.073 687 DIBUTYLTIN DICHLORIDE 0.011 0.4140.209 0.623 0.559 0.431 0.126 688 DIBUTYLTIN DIACETATE 0.012 0.525 0.3240.501 0.775 0.424 0.107 689 DIETHYL(3-PYRIDYL)BORANE 0.008 0.392 0.0180.654 0.752 0.433 0.249 690 DIMESITYLBORON FLUORIDE 0.330 0.237 0.4710.685 0.759 0.478 0.249 691 DIPHENYLZINC 0.011 0.431 0.242 0.499 0.5710.432 0.635 692 INDIUM(III) TRIFLUOROMETHANESULFONATE 0.494 0.094 0.5980.532 0.767 0.445 0.257 693 LITHIUM TRIFLUOROMETHANESULFONATE 0.0180.532 0.019 0.694 0.765 0.451 0.152 694 SODIUM TETRAPHENYLBORATE 0.2370.081 0.046 0.610 0.775 0.494 0.183 695 TIN(II) ACETATE 0.015 0.2330.385 0.453 0.454 0.416 0.089 696 TIN(II) BROMIDE 0.104 0.461 0.4100.548 0.430 0.423 0.112 697 TIN(II) FLUORIDE 0.001 0.568 0.028 0.6480.734 0.439 0.179 698 TRIMESITYLBORANE 0.014 0.536 0.032 0.645 0.7250.456 0.258 699 TRIS(4-ETHOXYPHENYL)BISMUTH 0.019 0.095 0.035 0.6200.742 0.438 0.145 700 TRIS(DIMETHYLAMINO)BORANE 0.002 0.109 0.022 0.6390.735 0.421 0.116 701 ZINC(II) BROMIDE 0.381 0.104 0.291 0.588 0.5190.436 0.211 702 ZINC(II) CHLORIDE 0.207 0.106 0.196 0.538 0.483 0.4340.121 703 1-NAPHTHALENEBORONIC ACID 0.010 0.090 0.044 0.706 0.795 0.5170.092 704 PHENYLBORONIC ACID 0.011 0.082 0.204 0.622 0.688 0.522 0.147705 TRIPHENYLBISMUTH 0.015 0.054 0.025 0.560 0.719 0.429 0.248 706SAMARIUM(II) IODIDE 0.030 0.100 0.028 0.504 0.411 0.438 0.156 707 SODIUMTETRAKIS(P-TOLYL)BORATE 0.064 0.327 0.024 0.703 0.839 0.470 0.142 708AMMONIUM CERIUM(IV) NITRATE 0.019 0.094 0.026 0.609 0.425 0.440 0.123709 2-METHOXY PHENYLBORONIC ACID 0.009 0.121 0.392 0.690 0.762 0.4900.120 710 4-FLUOROPHENYL BORONIC ACID 0.049 0.825 0.144 0.705 0.7570.528 0.109 711 4-METHOXYPHENYL BORONIC ACID 0.016 0.574 0.121 0.7320.786 0.494 0.104 712 ALUMINUM ACETYLACETONATE 0.017 0.088 0.019 0.6440.664 0.432 0.115 713 ALUMINUM HEXAFLUOROACETYLACETONATE 0.153 0.4790.562 0.654 0.716 0.445 0.071 714 ALUMINUM TRIFLUOROMETHANESULFONATE0.021 0.078 0.027 0.633 0.594 0.422 0.105 715DIMETHYLANILINIUMTETRAKIS(PENTAFLUORO PHENYL)BORATE 0.210 0.852 0.5480.638 0.713 0.403 0.308 716 LITHIUMTETRAKIS(PENTAFLUOROPHENYL) BORATEDIETHERATE 0.064 0.967 0.037 0.667 0.736 0.461 0.138 717 YTTERBIUM (III)TRIFLUOROMETHANESULFONATE HYDRATE 0.672 0.094 0.242 0.660 0.484 0.4530.087 718 TIN(II) ACETYLACETONATE 0.079 0.253 0.424 0.358 0.450 0.4230.233 719 TIN (II) HEXAFLUOROACETYLACETONATE 0.231 0.260 0.608 0.4290.417 0.431 0.372 720 P-TOLYLBORONIC ACID 0.010 0.632 0.221 0.669 0.7490.509 0.128 721 TRIS(4-TOLYL)BISMUTH 0.016 0.191 0.028 0.689 0.736 0.4280.143 722 TRIPHENYL ALUMINUM 0.670 0.370 0.418 0.664 0.513 0.430 1.036723 ALUMINUM (III) PHENOXIDE 0.003 0.552 0.039 0.664 0.774 0.452 0.420724 CERIUM(III) FLUORIDE 0.002 0.597 0.038 0.603 0.714 0.435 0.177 725COPPER(I) BROMIDE 0.047 0.279 0.133 0.625 0.463 0.449 0.217 726COPPER(I) CHLORIDE 0.009 0.193 0.147 0.683 0.517 0.464 0.158 727COPPER(I) IODIDE 0.118 0.642 0.030 0.655 0.684 0.453 0.136 728COPPER(II) ACETATE 0.007 0.201 0.010 0.663 0.686 0.418 0.055 729COPPER(II) BROMIDE 0.009 0.091 0.015 0.661 0.419 0.429 0.088 730COPPER(II) CHLORIDE 0.005 0.185 0.012 0.741 0.435 0.419 0.111 731COPPER(II) TRIFLUOROMETHANESULFONATE 0.018 0.061 0.022 0.739 0.833 0.4590.065 732 SAMARIUM(III) CHLORIDE 0.003 0.437 0.140 0.699 0.727 0.4320.143 733 TIN(II)TRIFLUOROMETHANESULFONATE 0.849 0.084 0.661 0.421 0.5300.442 0.106 734 YTTRIUM(III) CHLORIDE 0.151 0.101 0.060 0.442 0.3510.377 0.212 735 ZINC(II) TRIFLUOROMETHANESULFONATE 0.651 0.364 0.5290.652 0.599 0.444 0.172 736 YTTRIUM(III) TRIFLUOROMETHANESULFONATE 0.5610.105 0.234 0.723 0.564 0.463 0.169 737 TIN(II) OXIDE 0.002 0.656 0.0280.699 0.766 0.450 0.145 738 TRIFLUOROMETHANESULFONIMIDE 0.014 0.2990.019 0.714 0.760 0.438 0.107 739 CALCIUM(II) TRIFLUOROMETHANESULFONATE0.335 0.101 0.057 0.728 0.783 0.454 0.125 740 CERIUM(III) CHLORIDE 1.0280.091 0.491 0.635 0.418 0.167 0.202 741 COPPER(II) CHLORIDE 0.008 0.0720.014 0.780 0.428 0.444 0.085 742 COPPER(II) TRIFLUOROMETHANESULFONATE0.018 0.065 0.017 0.709 0.844 0.449 0.086 743 LANTHANUM(III) CHLORIDE1.143 0.085 0.634 0.643 0.469 0.448 0.133 744 LANTHANUM(III)TRIFLUOROMETHANESULFONATE 0.420 0.124 0.332 0.613 0.726 0.417 0.116 745MAGNESIUM(II) TRIFLUOROMETHANESULFONATE 0.342 0.125 0.499 0.644 0.7440.458 0.129 746 SCANDIUM(III) TRIFLUOROMETHANESULFONATE 0.469 0.0820.401 0.637 0.270 0.444 0.118 747 TIN(II) TRIFLUOROMETHANESULFONATE0.681 0.094 0.933 0.464 0.507 0.440 0.090 748 TRIETHANOLAMINE BORATE0.010 0.128 0.013 0.494 0.583 0.426 0.081 749 SAMARIUM(III)TRIFLUOROMETHANESUFFONATE 0.717 0.095 0.599 0.727 0.685 0.455 0.124 750SODIUM TETRAKIS(1-IMIDAZOYL)BORATE 0.012 0.746 0.019 0.476 0.432 0.4370.120 751 YTTRIUM(III) TRIFLUOROMETHANESULFONATE 0.506 0.091 0.313 0.7510.563 0.468 0.111 752 TRIFLUOROMETHANESULONIMIDE 0.012 0.363 0.017 0.7380.779 0.446 0.077 753 TIN(II) ACETYLACETONATE 0.006 0.079 0.011 0.4510.361 0.430 0.104 754 LANTHANIUM(III) TRISTRIFLUOROACETATE 0.882 0.1300.428 0.489 0.720 0.427 0.200 755 SAMARIUM(III) CHLORIDE 0.015 0.2670.270 0.421 0.418 0.438 0.138 756 TIN(II) FLUORIDE 0.018 0.581 0.3500.616 0.755 0.440 0.169 757 YTTRIUM(III) TRIFLUOROMETHANESULFONATE 0.2770.107 0.248 0.699 0.536 0.465 0.105 758 CALCIUM(II)TRIFLUOROMETHANESULFONATE 0.020 0.300 0.085 0.712 0.745 0.457 0.140 759LITHIUM TETRAKIS(PENTAFLUOROPHENYL) BORATE DIETHERATE 0.074 0.233 0.0280.700 0.709 0.469 0.199 760 SODIUMTETRAKIS(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BORATE 0.094 0.135 0.068 0.6640.753 0.442 0.191 761 DIMETHYLANILINIUMTETRAKIS(PENTAFLUOROPHENYL)BORATE 0.220 0.167 0.431 0.662 0.758 0.4330.114 762 [AliBu2(Et2O)] + [B(C6F5)3R]−^(a) 1.689 0.232 1.640 0.7830.798 0.785 1.356 763 Li[Al(OC6F5)4]^(b) 0.747 0.049 0.121 0.646 0.6170.429 0.238 764 AlMes3THF^(c) 0.395 0.090 0.316 0.297 0.383 0.424 0.301765 AlMe(2,6-t-Bu-4-Me(OC6H2))2^(d, g, h) 0.450 0.462 0.846 0.654 0.6080.421 0.303 766 Al-i-Bu2(OC6F5)^(e) 1.132 0.247 1.385 0.720 0.799 0.2990.630 767 NO ADDITIVE 0.011 0.502 0.032 0.686 0.755 0.412 0.249 768TRITYL TETRAKIS(3,5-BIS(TRIFLUOROMETHYL)PHENYL)BORATE^(f, i) 0.174 0.4470.049 0.680 0.829 0.571 0.208 769 TRIPHENYLBORON 0.610 0.648 0.685 0.6250.429 0.268

[0463] TABLE 68 Copolymerization Using 0.02 mmole Catalyst, 40 eq B(C₆F₅)₃, 8 mL TCB, 2 mL HA, at 120° C. under 6.9 MPa E for 18 h Yield#Me/ Mole % m.p. Ex Catalyst Sm(OTf)₃ (g) 1000 CH₂ Comonomer (° C.)(ΔH_(f)) Mw/PDI 770 5 1 eq 1.429 28 0.6 118 (96.0) 9,859/8.8 771 21 1 eq8.184 31 1.28 (¹³C) 112 (182.7) 1,628/2.4 0.40 IC 0.88 EG 772 39 0 eq0.216 28 0.8 111 (158.3) Bimodal 97 First 497,946/2.3 Second MP = 887

[0464] TABLE 69 Copolymerization Using 0.002 mmole Catalyst, 40 eqB(C₆F₅)₃, 20 eq LiB(C₆F₅)₄, 8 mL TCB, 2 mL HA, at 120° C. under 6.9 MPaE for 18 h m.p. Yield #Me/ Mole % (° C.) Ex Catalyst (g) 1000CH₂Comonomer (ΔH_(f)) Mw/PDI 773 5 3.998 10 0.54 (¹³C) 124 3,567/2.2 0.25IC (209.5) 0.29 EG 774 7 1.075 19 0.38 (¹³C) 112 1,405/1.8 0.19 IC(191.2) 0.19 EG 775 6 1.253 13 0.53 (¹³C) 122 11,123/10.8 0.25 IC(190.6) 0.28 EG 776 2 0.461 9 0.41 (¹³C) 125 22,311/10.8 0.20 IC (186.6)0.21 EG 777 26 0.897 11 0.61 (¹³C) 118 3,595/2.1 0.39 IC (172.3) 0.22 EG

[0465] TABLE 70 ¹³C NMR Branching Analysis for EGPEA Copolymers TotalHex+ Am+ Bu+ Ex Me Me Et Pr Bu & EOC & EOC & EOC 773 10.0 1.8 1.3 0.11.5 8.4 6.7 6.8 774 18.7 3.8 1.8 0.4 0.7 11.6 11.7 12.8 775 12.7 2.0 1.60.4 0.7 7.9 8.2 8.6 776 9.2 1.8 2.0 0.5 1.4 7.8 4.3 4.9 777 11 1.5 2.50.4 1.1 8.2 6.9 6.8

Example 778 Synthesis of 118

[0466] In a drybox, 0.300 g 40 and 0.487 g tris(3,5-bis(trifluoromethyl))borane were dissolved in 25 mL toluene. This mixturewas allowed to stir at RT for 1 h. The mixture was filtered throughCelite® and the solvent was evaporated. Brown solid (0.160 g) wasobtained. A single crystal was obtained by slowly evaporate themethylene chloride/heptane solution of 40. X-Ray single crystal analysisconfirmed the Zwitterionic structure of this catalyst. TABLE 71Copolymerization Using 0.02 mmole Catalyst, with a Total Vol- ume of 10mL of TCB and Polar Monomer, at 80° C. under 3.4 MPa of Ethylene PolarPolar Monomer Yield Ex. Catalyst B(C₆F₅)₃ Monomer Volume (mL) (g) 779 240 eq

2 0.010 780 118   0 eq

3 0.345 781 2 40 eq CH₂═CH(CH₂)₂C(O)CH₃ 3 0.020 782 2 40 eq

3 0.556 783 2 40 eq CH₂═CH(CH₂)₇C(CH₂O)₃CCH₃ 3 10.26 9

[0467] TABLE 72 Ethylene Polymerization Using 0.01 mmole Catalyst, 20 eqLiB(C₆F₅)₄, 10 mL TCB, at 60° C. under 3.4 MPa Ethylene for 18 h Yield#Me/ m.p. Ex Catalyst (g) 1000CH₂ (° C.) (ΔH_(f)) Mw/PDI 784  2 1.842  8126 (166.2) 35,425/2.8 785  6 1.698  5 128 (172.7) 43,111/2.2 786  54.377 16 123 (173.9) 17,351/3.0 787  7 9.143 70 105 (157.2)  1,636/4.3788 30 0.281 17 123 (195.5) 12,383/9.6

[0468] TABLE 73 Ethylene/CO Copolymerization Using 0.02 mmole Catalyst,40 eq B(C₆F₅)₃, 10 mL TCB, at 100° C. under 2.8 MPa Ethylene/CO (9:1molar ratio) for 16 h Ex Catalyst Yield (g) 789 21  0.345 790 2 0.108791 5 0.201 792 4 0.024 793 40  0.480

[0469] Syntheses of these compounds will be found in previouslyincorporated U.S. patent application ______ (filed concurrently May 31,2001, Applicant's reference CL1655 US NA) and U.S. Provisional PatentApplication ______ (filed concurrently May 31, 2001, Applicant'sreference CL1744 US PRV1)(incorporated by reference herein for allpurposes as if fully set forth). TABLE 74 Copolymerization Using 0.02mmole Catalyst, 40 eq B (C₆F₅)₃, 6 mL TCB, 4 mL HA, at 100° C. under 6.9MPa E for 18 h Yield #Me/ Mole % HA m.p., (° C.) TON Ex. Catalyst (g)1000 CH₂ in Polymer [ΔH_(f)] Mw/PDI E/HA 794 120 2.067* 24 3.9 106 [120]7,664/2.3 3,009/121

[0470] TABLE 75 Copolymerization Using 0.02 mmole Catalyst, 40 eq B(C₆F₅)₃, 6 mL TCB, 4 mL HA, or EGPEA at 120° C. under 6.9 MPa E for 18 hCo- Monomer Yield #Me/ m.p. TON Ex. Catalyst (Mole %) (g) 1000 CH₂ (°C.) [ΔH_(f)] Mw/PDI E/Comonomer 795 120 HA 2.543*  29  97 [86.3]6,688/2.7 3,587/170 (4.4) 796 120 EGPEA 3.182** 22 100 [88.8] 9,821/3.34,989/100 (2.0)

[0471] TABLE 76

E/HA Copolymerization Using 0.02 mmole Catalyst, 40 eq B(C₆F₅)₃, , 20 eqLi B(C₆F₅)₄, 6 mL TCB, 4 mL HA, at 100° C. under 6.9 MPa E for 18 h Mole% HA Yield #Me/ TON Ex. Catalyst in Polymer (g) 1000 CH₂ m.p. (° C.)(ΔH_(f)) Mw/PDI E/Comonomer 797 121 23 0.356^(a) 13 122 (138.6) 4,864/2.6 477/11 798 126 0.2^(b) 0.403^(c)  3 126 (181.4) 19,918/8.0659/6 

[0472] TABLE 77 Copolymerization Using 0.02 mmole Catalyst, 40 eqB(C₆F₅)₃, 20 eq Li B(C₆F₅)₄, 8 mL TCB, 2 mL HA, at 100° C. under 6.9 MPaE for 18 h Mole % HA Ex. Catalyst Yield (g)^(a) #Me/1000CH₂ in Polymerm.p. (° C.) (ΔH_(f)) Me/PDI 799 121 1.750 27 0.8 124 (160.1)10,049/3.47  800 122 1.710 26 1.2 118 (176.1) 3,422/2.42 801 123 0.83434 1.8 120 (147.9)  3,605/1,521 802 124 0.478 52 2.2  95 (132.9)2,392/2.37 803 125 0.804 36 1.8 119 (153.5) 3,275/2.40 804  127^(b)4.257  8 1.1 123 (158.1) 7,725/1.97

Examples 805-833

[0473] The reaction mixture including catalyst, solvent, acrylate andcocatalysts was assembled inside a nitrogen filled drybox and placed ina 50 mL stainless steel pressure vessel. A stir bar was added and thevessel sealed and removed from the drybox where it was pressurized withethylene to the desired pressure. The vessel was heated and stirred witha constant pressure of ethylene for the duration of the reaction.

TABLE 78 Mol % Ex. Catalyst mmol Ni NaBArf eq B(C₆F₅)₃ eq C₆H₅Cl mLEGPEA mL Time h Temp Yield Kg/g Ni Mw EGPEA 805 45 0.001659 166 767 151.5 66 ˜127° C.   15.74 161 13761 0.36/0.40 806 45 0.001875 150 680 15.5MA 1.0 18 ˜124° C.   4.65 42 0.43 807 45 0.0015 188 850 15 2.1 63 125°C. 10.9 124 0.45/0.47 808 45 0.0015 188 850 15 1.5 63 117° C. 3.3 389948 0.7 809 76 0.0015 188 850 15 1.5 17 125° C. 2.3 26 19213 0.6 810 760.0015 188 850 15 1.5 17 120° C. 1.9 22 30124 low 811 128 0.0015 188 85015 1.5 17  80° C. 4.5 51 39600 low (0.2-0.3) 812 128 0.00075 380 1700 17 2.1 18  82° C. 1.34 31 low 813 74 0.00125 225 1017  15 tol. MA 1.0 66120° C. 2.82 38 814 45 0.0015 188 850 15 1.5 18 120° C. 4.65 51 127580.5 815 45 0.0015 188 850 15 MA 1.0 72 123° C. 7.3 83 32036 0.24 (13C)816 128 0.0015 188 850 15 MA 1.0 72 100° C. 4.2 48 13082 0.29 (13C) 81751 0.0015 188 850 15 1.5 18 120° C. 0.7 8 20294 0.3 818 45 0.0015 188850 (Al + B−)^(a) 15 1.5 18 120° C. 4.1 47 12133 0.3 819 45 0.0015 188430 (Al + B−)^(a) 16 1.5 18 120° C. 2.8 32 14634 0.6 820 45 0.0015 188850 15 1.5 18 122° C. 3.5 40 821 45 0.0015 188 850 15 MA 2 66 122° C.8.5 97 13162 0.41 (13C) 822 45 0.0015 188 850 15 MA 3 17 123° C. 4.9 568305 0.88 (13C) 823 74 0.0015 188 850 15 MA 2 125 125° C. 4.1 47 23003824 45 0.0015 188 MAO 1 ml 15 1 18 125° C. 4.4 50 10011 Low 825 450.0015 188 MAO 0.3 ml 15 1.5 18 100° C. 4.2 48 0.29 826 45 0.0015  188LiB^(b) 850 15 1.5 18 122° C. 2.9 33 0.53 827 45 0.0015 188 LiB MAO 0.2ml 15 1.5 18 100° C. 1 11 12507 0.52 828 45 0.0015 188 LiB MAO 0.3 ml 151.5 18 100° C. 1.3 15 11851 0.63 829 45 0.0015 188 MAO 0.3 ml 15 1.5 18100° C. 6.6 75 20849 0.27 830 74 0.0015 188 1300 15 MA 3 115 120° C. 3.439 15103 0.56 831 40 0.00166 170 766 15 1.5 18 ˜118° C.   5.94 61 0.5*832 21 0.00166 170 766 16 1.5 18 ˜125° C.   3.74 38 ˜0.5 833 40 0.0015188 850 15 1.5 66 123° C. 5.2 59 1.2*

Examples 829-846

[0474]

[0475] Preparation of Supports

[0476] Support A: Inside a nitrogen filled drybox, dehydrated,spray-dried spherical silica (2g, Grace XPO-2402, dehydrated to ˜1 mmolOH/g silica) was placed in 6 mL dry toluene and AlMe3 (3 mL, 2M inhexane, Aldrich) added. The slurry was agitated by shaking for 30 minafter which the solids were filtered, washed with pentane and driedunder vacuum.

[0477] Support B: Inside a nitrogen filled drybox, spray-dried sphericalsilica-alumina (1 g, Grace MS 13-1.10, dehydrated at 500° C.) was placedin 6 mL dry toluene and AlMe₃ (1.8 mL, 2M in hexane, Aldrich) added. Theslurry was agitated by shaking for 30 min after which the solids werefiltered, washed with pentane and dried under vacuum.

[0478] Preparation of Catalysts

[0479] Catalyst I: Support A (0.5 g) was added to a solution of 45 (76mg, 0.05 mmol) in anhydrous toluene. The slurry was agitated by shakingfor 30 min after which the solids were filtered away from the brownfiltrate and dried under vacuum.

[0480] Catalyst II: Silica supported MAO (Albemarle Corp, 18 wt % Al onspherical silica) was added to a solution of 45 (76 mg, 0.05 mmol) andB(C₆F₅)₃ (0.133 g, 5 eq) in anhydrous toluene. The slurry was agitatedby shaking for 30 min after which the solids were filtered away from theblack/brown filtrate and dried under vacuum. ICP: % Ni=0.43%.

[0481] Catalyst III: Support A (0.5 g) was added to a solution of 45 (76mg, 0.05 mmol) and B(C₆F₅)₃ (0.133 g, 5 eq) in anhydrous toluene. Theslurry was agitated by shaking for 30 min after which the solids werefiltered away from the green/brown filtrate and dried under vacuum. ICP:% Ni=0.42%.

[0482] Catalyst IV: Inside a nitrogen filled drybox, spray-driedspherical silica alumina (0.5 g, Grace MS 13-1.10, dehydrated at 500° C.under flowing N₂), was placed in anhydrous toluene (8 mL) and 45 (38 mg,0.025 mmol) added. The slurry was agitated by shaking for 30 minutesafter which the orange brown solids were filtered, washed with tolueneand finally pentane and dried under vacuum. ICP: % Ni=0.28%.

[0483] Catalyst V: Inside a nitrogen filled drybox, spray-driedspherical silica alumina (0.5 g, Grace MS 13-1.10, dehydrated at 500° C.under flowing N₂), was placed in anhydrous methylene chloride (8 mL) and129 (16 mg, 0.022 mmol) added. The slurry was agitated by shaking for 45min after which the orange solids were filtered, washed with toluene andfinally pentane and dried under vacuum. ICP: % Ni=0.24%.

[0484] Catalyst VI: Support B (0.25 g) was added to a solution of 45 (19mg, 0.013 mmol) in anhydrous toluene. The slurry was agitated by shakingfor 45 min after which the solids were filtered away from the dark greenfiltrate, washed with toluene and dried under vacuum.

[0485] Catalyst VII: Support A (0.25 g) was added to a solution of 45(19 mg, 0.013 mmol in anhydrous toluene. The slurry was agitated byshaking for 45 min after which the solids were filtered away from thelight brown filtrate, washed with toluene and dried under vacuum.

[0486] Catalyst VIII: Silica supported MAO (0.25 g, Albemarle, 18 wt %Al) was added to a toluene solution of 45 (19 mg, 0.013 mmol in 10 mL).The slurry was agitated by shaking for 30 min after which the solidswere filtered away from the blue filtrate, washed with toluene and driedunder vacuum. ICP; % Ni=0.36%.

[0487] Catalyst IX: Support B (0.25 g) was added to a solution of 45 (19mg, 0.013 mmol) in anhydrous toluene. B(C₆F₅)₃ (56 mg, BoulderScientific) was added and the slurry was agitated by shaking for 30 minafter which the solids were filtered away from the brown filtrate,washed with toluene and dried under vacuum. ICP % Ni=0.28%.

[0488] Catalyst X: Support A (0.25 g) was added to a solution of 45 (19mg, 0.013 mmol) in anhydrous toluene. The slurry was agitated by shakingfor 60 min after which the brown solids were filtered away from thegreen filtrate, washed with toluene and dried under vacuum.

[0489] Catalyst XI: Support A was added to a solution of 45 (19 mg,0.013 mmol) in anhydrous toluene. The slurry was agitated by shaking for60 min after which the orange solids were filtered away from the orangefiltrate, washed with toluene and dried under vacuum.

[0490] Catalyst XII: Support A (0.25 g) was added to a solution of 129(9.6 mg, 0.013 mmol) in anhydrous toluene. The slurry was agitated byshaking for 60 min after which the gray solids were filtered away fromthe purple filtrate, washed with toluene and dried under vacuum.

[0491] Catalyst XIII: Support A (0.25 g) was added to a solution of 40(5.6 mg, 0.013 mmol) in anhydrous toluene. The slurry was agitated byshaking for 60 min after which the orange solids were filtered away fromthe orange filtrate, washed with toluene and dried under vacuum.

[0492] Catalyst XIV: Support A (0.25 g) was added to a solution of 21(4.5 mg, 0.013 mmol) in anhydrous toluene. The slurry was agitated byshaking for 60 min after which the beige solids were filtered away fromthe filtrate, washed with toluene and dried under vacuum.

[0493] Copolymerization of ethylene with EGPEA

[0494] The solid catalyst and cocatalyst components (catalyst ˜0.004mmol, 0.177 g NaBAF, and optionally B(C₆F₅)₃) were added to a glassinsert. Solvent (anhydrous chlorobenzene, 9 mL) and EGPEA, (1 mL,filtered through basic alumina, Aldrich) were added last and the insertplaced in a metal pressure vessel. Some ethylene was admitted and thevessel was heated to 120° C. and then pressurized to 6.9 MPa withethylene and agitated for 18 h. After this time the reactor was cooled,the pressure released and the contents of the insert placed in stirringmethanol to precipitate polymer product. The polymeric product was thenfiltered, washed well and dried. Results are given in Table 79. TABLE 79B(C₆H₅)₃ AlMe(BHT)₂ % EGPEA³ in- Ex Catalyst (mg) 98 eq 20 eq Yield (g)corporated kg PE/g Ni¹ 829 45 (5.8 mg)⁴ 0.2 g — 6.6 0.5 28 830 45 (5.8mg)⁴ 0.2 g 40 mg 5.4 0.5 23 831 45 (5.8 mg)⁴ — 40 mg 2.7  0.7² 11 832VIII (77 mg) — — 0.6 0.4 3 833 I (40 mg) 0.2 g 3.4 0.5 14 834 IV (77 mg)0.2 g 5.3 0.4 22 835 V (77 mg) 0.2 g 2.1 0.5 9 836 X (80 mg) 0.2 g — 3.60.7 15 837 XI (80 mg) — 40 mg 3.0  0.8² 13 838 XII (80 mg) — 40 mg 2.1 0.9² 9 839 XIII (80 mg) — 40 mg 6.9 0.5 29 840 XIV (80 mg) — 40 mg 0.10.3 0.5

[0495] Inside a nitrogen filled drybox the solid catalyst and cocatalystcomponents (2.5 mg NaBAF, and optionally B(C₆F₅)₃) were added to glassinserts. Solvent (anhydrous chlorobenzene, 0.25 mL) and EGPEA, (0.05 mL,filtered through basic alumina, Aldrich) were added last and the insertsplaced in a metal pressure vessel. The vessel was sealed, removed fromthe drybox and placed under an atmosphere of ethylene at 6.9 MPa andheated to 110-120° C. for 16 h. After cooling the vessel was opened andthe reactions quenched with methanol, and the polymeric productfiltered, washed with methanol and dried. Results are given in Table 80.TABLE 80 Yield % EGPEA³ in- End Groups Ex. Catalyst (mmol) (mg)corporated Int:Term. 841 45¹ (0.002) 0.36 1.5 9:1   842 II (0.002) 0.131.3 1:1.1 843 III (0.002) 0.13 1.9 1:1.1 844 45¹ (0.001) 0.22 1.5 2:1  845 VI (0.001) 0.08  1.9² 1:1.3 846 VII (0.001) 0.07 1.2 1:1.3

Examples 847-850 General Procedure for Polymerizations in Tables 81-86

[0496] The polymerizations were carried out according to GeneralPolymerization Procedure A. Varying amounts of acrylate homopolymer arepresent in some of the isolated polymers. For acrylate copolymers, theyield of the polymer is reported in grams and includes the yield of thedominant ethylene/acrylate copolymer as well as the yield of any crylatehomopolymer that was formed. Molecular weights were determined by GPC,unless indicated otherwise. Mole percent acrylate incorporation andtotal Me were determined by ¹H NMR spectroscopy, unless indicatedotherwise. Mole percent acrylate incorporation is typicallypredominantly IC, unless indicated otherwise. The LiB(C₆F₅)₄ used(LiBArF) included 2.5 equiv of Et₂O.

[0497] 2,6-Bis-dimethoxyphenyllithium was prepared from 14.18 g (0.103mole) of 1,3-dimethoxybenzene, 77 mL of a 1.6 M solution of BuLi inhexanes and 0.23 mL of N,N,N′,N′-tetramethylethylenediamine in drydiethyl ether (72 mL). Dichloromethylphosphine (5.0 g, 0.04276 mole) wasadded at 0° C., and the reaction mixture was stirred at room temperatureovernight. Methanol (20 mL) was added, and the mixture was concentratedto about half its original volume under reduced pressure. The resultingwhite precipitates were filtered and were recrystallized from methanolto give white crystals of bis-(2,6-dimethoxyphenyl)(methyl)-phosphinewith 48% yield (6.6 g) and melting point at 112.33° C. ¹H NMR (CDCl₃) δ1.75 (s (broad), 3H, Me—P), 3.55 (s, 12H, Me—O), 6.4- 7.2 (m, 6H,aromatic protons); ³¹p NMR (CDCl₃) δ - 51.5 ppm. LS/MS: found m/w is321, calculated m/w is 321. Anal. found: C 64.30%; H 6.45%; calculatedfor C₁₇H₂₂O₄P: C 63.49%; H 6.85%.

[0498] Synthesis of A-3.Bis-(2,6-dimethoxyphenyl)phosphino]-methyllithium (2,6-MeO—Ph)₂P—CH₂—Li)(0.33 g, 0.001 mole) was prepared from a 7 mL THF solution of equi-molaramounts of bis-(2,6-dimethoxyphenyl)-(methyl)phosphine and a 1.6 Msolution of butyllithium in hexanes with a catalytic amount of TMEDAadded. tert-Butylisocyanate (0.125 g, 0.001 mole) in 3 mL of THF wasadded to the reaction mixture, which was then stirred for 12 hours.Next, 0.24 g (0.0005 mole) of 2-methoxycarbonyl-allyl nickel bromidedimer [(CH₂═C(CO₂Me)CH₂)Ni(μ—Br)]₂ and 0.89 g (0.001 mole) of NaBAF in 4mL of THF was added to the reaction mixture, which was stirredovernight. The next day, the solvent was pumped off and the residue wasredissolved in diethyl ether. The solution was filtered through Celite®,and solvent was removed under vacuum. Viscous brown product (0.92 g) wasobtained. ³¹P NMR (CD₂Cl₂) one major peak at 26.49 ppm.

[0499] Synthesis of A-1 and A-4. Synthesis was in a fashion analogous tothat reported for A-3 in above, except that (t-Bu)₂PCH₂Li was employedas the base for the synthesis of A-1 and different electrophiles wereemployed. The electrophiles employed and compound characterizationfollow: ³¹P NMR^(a) (CD₂Cl₂) Cmpd Electrophile δ A-1 2,4-Dimethoxy- 60.6ppm (major); phenylisocyanate 62.1 ppm (minor) A-4 2,4,6-Trimethoxy-22.5 (major) benzophenone

[0500] TABLE 81 Ethylene Homopolymerizations and Ethylene/Acrylate Co-polymerizations (18 h) Acrylate Cmpd Acrylate mL B(C₆F₅)₃ Press TempYield Incorp. Total Ex (mmol) (Solvent mL) (Borate) MPa ° C. g mol %M.W. Me 847 A-1 EGPEA 1 100 3.4 60 0.64 0.5 M_(p) = 13,148; 7.1 (0.004)(p-Xylene equiv 0.3 IC M_(w) = 14,087; 9) (NaBAF 0.2 EG M_(n) = 6,487;50 PDI = 2.17 equiv) 848 A-1 EGPEA 1 20 equiv 1 60 0.09 1.4 M_(p) =5,447; 13.3 (0.02) (p-Xylene (NaBAF 0.7 IC M_(w) = 8,088; 9) 10 0.7 EGM_(n) = 3,454; equiv) PDI = 2.17 849 A-3 None 10 equiv 3.4 60 0.80 —M_(p) = 801; 119 (0.02) (p-Xylene (None) M_(w) = 37,894; 10) M_(n) =500; PDI = 75.77 850 A-4 None 10 equiv 3.4 60 0.33 — M_(p) = 956; 76.4(0.02) (p-Xylene (None) M_(w) = 52,382; 10) M_(n) = 817; PDI = 64.09

[0501] TABLE 82 Ethylene/Acrylate Copolymerizations (0.004 mmol Cmpd, 18h, 100 equiv B (C₆F₅)₃, 50 equiv LiB (C₆F₅)₄, 1 mL EGPEA, 9 mL p-Xylene)Acrylate Press Temp. Yield Incorp Total Ex Cmpd MPa ° C. g Mol % M.W. Me851 45 2.1 60 0.008 0.7 M_(n)(¹H): No Olefins 11.9 852 91 2.1 60 0.0081.5 M_(n)(¹H): No Olefins 13.6 853 94 2.1 60 0.011 1.2 M_(n)(¹H): NoOlefins 9.4 854 53 2.1 60 0.041 2.4 M_(n)(¹H) = 3,528.3 24.7 ^(a) 2.0 IC0.4 EG

[0502] TABLE 83 Ethylene/E-10-U Copolymerizations: Variation ofTemperature and Pressure (0.02 mmol Cmpd; 2 mL E-10-U; 8 mL TCB; 40equiv B(C₆F₅)₃; 18 h) Press Temp Yield Comonomer Ex Cmpd MPa ° C. gIncorp mol % M.W. 855 46 1 25 3.24 3.3 M_(p) = 67,355; M_(w) = 74,377;M_(n) = 39,452; PDI = 1.89 856 46 3.4 60 11.14 2.8 M_(p) = 67,243; M_(w)= 69,152; M_(n) = 34,553; PDI = 2.00 857 46 6.9 120 6.09 1.1 M_(p) =13,731; M_(w) = 20,516; M_(n) = 5,477; PDI = 3.75

[0503] TABLE 84 Ethylene/Zonyl TAN (ZTAN) Copolymerization (0.002 mmolCmpd; 200 equiv B (C₆F₅)₃; 100 equiv NaBAF; 18 h) ZTAN g Press TempYield Comonomer Total Ex Cmpd (p-Xylene mL) MPa ° C. g Incorp Mol % M.W.Me 858 45 2 6.9 120 17.90 Trace M_(p) = 11,579; Nd (8) M_(w) = 12,467;M_(n) = 4,226; PDI = 2.95 859 45 3 4.1 80 0.613 0.52 M_(p) = 24,805;20.3^(a) (7) (¹³C M_(w) = 23,507; (¹³C NMR) M_(n) = 10,500; NMR) PDI =2.24 860 45 3 6.9 100 1.75 0.30 M_(p) = 20,490; 27.4^(b) (0.002) (7)(¹³C M_(w) = 21,489; (¹³C NMR) M_(n) = 10,466; NMR) PDI = 2.05

[0504] TABLE 85 Ethylene/Acrylate/alpha-Olefin Terpolymerizations (0.002mmol Cmpd; 18 h; 6.9 MPa E; 120° C.; 8 mL p-Xylene; 200 equiv B (C₆F₅)₃;100 equiv NaBAF; alpha-Olefins: 1-Hexene, 1-H; Ethyl-10-Undecylenate,E-10-U) Acrylate α-Olefin Yield Acrylate E-10-U Total Ex Cmpd mL mL gIncorp^(a) mol % Incorp^(a) mol % Me^(a) 861 45 EGPEA 1-H 1.64 0.57 ^(b)57.2^(c) 1 1 862 45 EGPEA E-10-U 2.24 0.86 0.80 45.0^(d) 1 1 863 40EGPEA 1-H 6.33 0.51 ^(b) 11.7^(e) 1 1 0.23 IC 0.28 EG 864 40 EGPEAE-10-U 3.48 0.42 0.33  8.7^(f) 1 1 0.21 IC 0.21 EG

[0505] TABLE 86

Ethylene/Acrylate Copolymerizations (0.02 mmol Cmpd; 6.9 MPa E; 1 mLEGPEA; 9 mL TCB; 18 h) Comon- omer Borane Borate Temp Yield Incorp TotalEx Cmpd equiv equiv ° C. G mol % M.W. Me 865 H-1 B(C₆F₅) NaBAF 120 1.280.2 M_(p) = 5,017; M_(w) = 6,796; 54.3 ₃ 20 10 IC & EG M_(n) = 1,840;PDI = 3.69 866 H-2 BPh₃ none  80 0.14 5.3 Bimodal 22.0 20 UV: M_(p) =21,679; RI M_(p) = 20,271;

Example 867 - Synthesis of (t-Bu)₂PCH₂N(2,6-C₆F₂H₃)OLi

[0506]

[0507] In a dry box, to a 50 mL flask containing 10 mL of THF solutionof 1,3-difluoro-2-nitrosobenzene (0.0276 g, 0.193 mmol), was addedslowly to a THF solution of (t-Bu)₂PCH₂Li (0.0321 g, 0.193 mmol) at −30°C. The solution was stirred 2 hours and it turned brown. After removalof the solvent, the purple residue was rinsed with pentane and driedunder vacuum. A brown powder was obtained.

Example 868 - Synthesis of (t-Bu)₂PCH₂N(2-(3-OLi)C₁₀H₆)OLi

[0508]

[0509] In a dry box, to a 100 mL flask containing 20 mL of THF solutionof 2-nitroso-1-naphthol (0.1044 g, 0.603 mmol), NaH (0.016 g, 1.1equiv.) powder was added slowly at room temperature. When no more H₂ wasreleased, a THF solution of (t-Bu)₂PCH₂Li (0.1002 g, 0.603 mmol) at −30°C. was added slowly. The solution was stirred 2 hours and turned brownfrom yellow. After removing the solvent, a brown powder (0.1402 g, 0.388mmol) was obtained in 64% yield. ¹H NMR (C₆D₆): complicated. ³¹P NMR(C₆D₆): major peak 29.5636 ppm.

Example 869 - Synthesis of (t-Bu)₂PCH₂N(C₆H₅)OLi

[0510]

[0511] In a dry box, to a 100 mL flask containing 20 mL of THF solutionof nitrosobenzene (0.0682 g, 0.64 mmol), was added slowly a THF solutionof (t-Bu)₂PCH₂Li (0.1058 g, 0.64 mmol) at −30° C. The solution wasstirred overnight and turned purple from yellow. After removing thesolvent, a purple powder (0.1321 g, 0.483 mmol) was obtained in 76%yield. ¹H NMR (C₆D₆) : complicated; ³¹P NMR (C₆D₆): major peak 38.1167ppm.

Example 870 - Synthesis of (t-Bu)₂PCH₂N(2-CH₃-C₆H₄)OLi

[0512]

[0513] In dry box, to a 100 mL flask containing 20 mL of THF solution ofo-nitrosotoluene (0.0763 g, 0.63 mmol) was added slowly a THF solutionof (t-Bu)₂PCH₂Li (0.1046 g, 0.63 mmol) at −30° C. The solution wasstirred overnight and turned purple from yellow. After removing thesolvent and rinsing with pentane, a purple powder (0.1538 g, 0.54 mmol)was obtained in 85% yield. ¹H NMR (C₆D₆): complicated; ³¹P NMR (C₆D₆):complicated, indicating the desired product, but also additionalproducts.

Examples 871-874 - Polymerizations of Ethylene at 1000 psi of C₂H₄ inshaker tube:

[0514] Conditions: 0.02 mmol ligand, 1 equiv. Allyl-Ni complex, 10equiv. B(C₆F₅)₃, 5 ml TCB, RT, 18 h. TO (molPE/ Ex Ligand PE (g) mol cat871 1001 3.0595  5110.9 872 1002 7.9434 13827.2 873 1003 6.8919 13165.7874 1004 3.9511  7226.8

[0515] The syntheses of aminopyrrole ligands is published in WO00/50470.

Example 875 - Synthesis of Ligand 1005

[0516] A 50 mL round bottom flask was charged with 0.3988 g (2.745 mmol)of 40 wt. % glyoxal solution in water, 0.6045 g (5.49 mmol) of1-amino-2,5-dimethylpyrrole, 15 ml methanol and 1 drop of formic acid.The mixture was stirred overnight and light brown precipitate formed.The solid was collected by filtration, rinsed with hexane and driedunder vacuum. 0.46 g (1.9 mmol) of product was obtained in 69% yield. ¹HNMR (CDCl₃) δ 8.18 (s, 2, C—H), 5.8 (s, 4, Hpy) , 2.3 (s, 12, CH₃).

Example 876 - Synthesis of Ligand 1006

[0517] A 50 mL round bottom flask was charged with 0.25 g (2.9 mmol) of2,3-butadione, 0.696 g (6.318 mmol) of 1-amino-2,5-dimethylpyrrole, 20ml methanol and 1 drop of formic acid. The reaction was monitored by TLCwith elute of 10% ethyl acetate in hexane. Two major spots were showedon the TLC even after overnight stirring. The clear yellow mixture wasstirred 2 days and the solvent was removed. The yellow residue wasrecrystallized with hexane. 0.26 g (0.96 mmol) of bis-substitutedproduct and 0.3652 g (2.0 mmol) of mono-substituted product wereobtained. ¹H NMR (CDCl₃) for bis-: δ 5.83 (s, 4, Hpy), 2.12 (s, 6, CH₃),2.0 (s, 12, CH₃- Py). ¹H NMR (CDCl₃) for mono-: δ 5.83 (s, 4, H-py),2.52 (s, 3, CH₃), 1.96 (s, 12, CH₃- py), 1.92 (s, 3, CH₃)

Example 877 - Synthesis of Ligand 1007

[0518] A 150 mL round bottom flask was charged with 0.6 g (2.9 mmol) ofacenaphthenequinone, 0.6488 g (5.89 mmol) of1-amino-2,5-dimethylpyrrole, 50 ml methanol and 1 drop of formic acid.The reaction was monitored by TLC with elute of 30% ethyl acetate inhexane and stirred 3 days. The solvent was removed under vacuum and thered residue was separated on a silica gel column with 30% ethyl acetatein hexane. 0.07 g (0.19 mmol) of dark red crystals bis-substitutedproduct and 0.06 g (0.2 mmol) of orange powder mono-substituted productwere obtained. ¹H NMR (CDCl₃) for bis-: δ 7.96 (d, 2, H-acen), 7.5 (t,2, H-acen), 6.74 (d, 2, H-acen) , 5.99 (s, 4, H-py) , 2.08 (s, 12, CH₃ -Py) ¹H NMR (CDCl₃) for mono-: δ 8.17 (d-d, 2, H-acen), 8.08 (d, 1,H-acen), 7.8 (t, 1, H-acen), 7.54 (t, 1, H-acen), 6.91 (d, 1, H-acen) ,5.97 (s, 2, H-py) , 2.02 (s, 6, CH₃-Py). If the reaction was carried outin toluene with p-toluenesulfonic acid as catalyst under reflux, theexclusive product was bis-substituted but it was isolated in very lowyield.

Example 878 - Synthesis of Ligand 1008

[0519] A 50 mL round bottom flask was charged with 0.1418 g (1.65 mmol)of 2,3-butadione, 0.5478 g (3.29 mmol) of1-amino-2,5-diisopropylpyrrole, 20 ml methanol and 1 drop of formicacid. The reaction was monitored by TLC with elute of 10% ethyl acetatein hexane and stirred 2 days at 50° C. The solvent was removed undervacuum and the yellow oily residue was separated on a silica gel columnwith 5% ethyl acetate in hexane. 0.226 g (0.59 mmol) of yellowcrystalline product was obtained in 36% yield. ¹H NMR (CDCl₃) : 5.86 (s,4, H-py), 2.53 (m, 4, H-Pr-i), 2.11 (s, 6, CH₃)₂, 1.10 (d, 24, CH₃-Pr-i)

Example 879 - Synthesis of Ligand 1009

[0520] A 100 mL round bottom flask was charged with 0.4418 g (2.43 mmol)of acenaphthenequinone, 0.907 g (4.85 mmol) of1-amino-2-methyl-5-phenylpyrrole, 50 ml methanol and 1 drop of formicacid. The reaction was monitored by TLC with elute of 30% ethyl acetatein hexane and stirred 7 days at RT. The solvent was removed under vacuumand the red solid residue was separated on a silica gel column with 10%ethyl acetate in hexane. 0.15 g (0.30 mmol) of dark red crystals wereobtained in 13% yield. ¹H NMR (CD₂Cl₂) : δ 8.06 (m, 2H) , 7.72-7.6 (m,6H) , 7.32 (m, 4H), 7.18 (m, 2H), 6.92 (d, 1H), 6.86 (d, 1H), 6.66 (d-d,2H), 6.38 (d, 2H), 2.32 (d, 6, CH₃).

Example 880 - Synthesis of Ligand 1010

[0521] A 100 mL round bottom flask was charged with 0.1881 g (2.18 mmol)of 2,3-butadione, 0.817 9 (4.37 mmol) of1-amino-2-methyl-5-phenylpyrrole, 50 ml methanol and 1 drop of formicacid. The reaction was stirred 7 days at RT and yellow precipitateformed. The reaction mixture was filtered through a frit to collect theyellow solid that then was dissolved in ether and dried over Na₂SO₄. Theether was removed and the yellow solid was dried under high vacuum. 0.46g (1.17 mmol) yellow powder was obtained in 53% yield. ¹H NMR (CD₂Cl₂) :δ 7.20 (m, 8, Ph—H), 7.10 (t, 2, Ph—H), 6.20 (d, 2, Py—H), 5.95 (m, 2,Py—H), 2.05 (s, 6, CH₃), 1.80 (s, 6, CH₃)

Example 881 - Synthesis of Ligand 1011

[0522] A 100 mL round bottom flask was charged with 0.129 g (1.5 mmol)of 2,3-butanedione, 0.7021 g (3.0 mmol) of 1-amino-2,5-diphenylpyrrole,50 ml methanol and 1 drop of formic acid. The reaction was monitored byTLC with elute of 30% ethyl acetate in hexane and stirred 7 days at RT.The solvent was removed under vacuum and the red solid residue wasseparated on a silica gel column with 10% ethyl acetate in hexane.0.4963 g (0.97 mmol) of yellow powder was obtained in 64% yield. ¹H NMR(CD₂Cl₂): δ 7.37(m, 4, ph—H), 7.28 (m, 6, ph—H), 6.49 (s, 2, py—H), 1.76(s, 6, CH₃).

Example 882 - Synthesis of Catalyst 1012

[0523] The ligand 7 (0.1102 g, 0.212 mmol), allyl-Ni dimer(](2-MeO₂C—C₃H₄)NiBr]₂) (0.0505 g, 0.106 mmol) andNa(tetra[3,5-bis(trifluoromethyl)]-phenylborane) (0.1879 g, 0.212 mmol)were mixed in 20 mL of ether in a 50 mL of round bottom flask. Thereaction mixture was stirred at room temperature for one hour andfiltered through a Celite plug on a frit. Removal of the solvent yieldsa brown powder that was then rinsed with pentane and dried under highvacuum. 0.3069 g (0.199 mmol) product was collected in 94% yield. ¹H NMR(CD₂Cl₂) : δ 7.58-7.06 (m, 6, Ar—H), 6.46 (d, 2, Py—H), 6.40 (d, 2,Py—H), 3.65 (s, 2, allyl-H) , 3.42 (s, 3, MeO), 1.90 (s, 6, CH₃), 1.85(s, 2, allyl-H).

Examples 883-898 Copolymerization of Ethylene and Polar-Comonomers

[0524] Into a glass vial used for shaker reaction, were weighed 0.02mmol of the ligand, 1 equivalent of allyl-Ni dimer([(2-MeO₂C—C₃H₄)NiBr]₂) and 10 equivalent of NaBaf. 2 ml of ether wasadded into the vial and shaken well. After two hours during which timethe most of the ether was evaporated off, 20 equivalent oftri(pentafluorophenyl)-borane cocatalyst, 9 ml of 1,2,4-trichlorobenzeneand 1 ml of ethylene glycol phenyl ether acrylate was added into thevial. The vials were placed into a shaker tube, sealed, and taken outfrom the dry box. The shaker tube was connected to a high pressure,ethylene shaker reaction unit. Reaction conditions for polymerizationwere: 1000 psi ethylene, 120° C., 18 hours. TABLE 87 Results of shakertube copolymerizations Catalyst Polymer Produc- Comon. Peak MP yieldtivity Me/1000 Incorp. (° C.) Ex Ligand (g) (Kg/g) M_(w) M_(n)M_(n)/M_(w) CH₂ (Mol %) ΔH (J/g) 883 1007 1.4967 1.37 2482 992  2.5 29.20.35  89 broad 884 1006 1.0752 0.88 3586 1306  2.75 28.5 0.27 114shoulder 885 1008 2.3451 2.07 38156 20004  1.91 — Trace  86 shoulder 8861008 2.6151 2.75 22933 1106  20.74 — Trace  93  b  109 887 1011 1.51411.09 5371 1209  4.44 b — trace 127 shoulder 888 1009 2.674 2.24 27541082  2.55 b trace  66 158 889 1010 1.6429 1.33 3860 1166  3.31 b trace117 shoulder 890 100 70.6397 0.78 20928 2232  9.37 b trace 120 shoulder891 1009 0.6282 0.53 208622 1615 129.15 b  85 bimodal broad 892 10100.7601 0.61 4855 1644  2.95 b 110 broad 893 1012 1.4557 1.22 16467 1116 14.76 b 125 160 894 1012 1.2511 1.06 17343 844  20.55 b — Trace 124  154.0 895 1007 1.1725 1.38 2832 1207  2.35 b 120 shoulder 896 10061.5382 0.97 29780 1160  25.68 — 0.15 122 185 897 1008 2.0138 2.08 144661293  11.19 — trace 898 1012 1.8074 1.56 54346 1881  28.9 — 0 125shoulder

What is claimed is:
 1. A process for the polymerization of olefins,comprising the step of contacting, at a temperature of about −100° C. toabout +200° C., at least one polymerizable olefin with an activepolymerization catalyst comprising a Group 3 through 11 (IUPAC)transition metal or a lanthanide metal complex of a ligand of theformula (I), (II) or (XII)

wherein: R¹ and R² are each independently hydrocarbyl, substitutedhydrocarbyl or a functional group; Y is CR¹¹R¹², S(T), S(T)₂, P(T)Q,NR³⁶ or NR³⁶NR³⁶; X is O, CR⁵R⁶ or NR⁵; A is O, S, Se, N, P or As; Z isO, Se, N, P or As; each Q is independently hydrocarbyl or substitutedhydrocarbyl; R³, R⁴, R⁵, R⁶, R¹¹ and R¹² are each independentlyhydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group; R⁷is hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group,provided that when Z is O or Se, R⁷ is not present; R⁸ and R⁹ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group; R¹⁰ is hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group; each T is independently ═O or ═NR³⁰; R³⁰ ishydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;R³¹ and R³² are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; R³³ and R³⁴ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that each isindependently an aryl substituted in at least one position vicinal tothe free bond of the aryl group, or each independently has an E_(s) of−1.0 or less; R³⁵ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that when A is O, S or Se, R³⁵ is notpresent; each R³⁶ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; m is 0 or 1; s is 0 or 1; n is 0 or1; and q is 0 or 1; and provided that: any two of R³, R⁴, R⁵, R⁶, R⁸ ,R⁹, R¹¹ and R¹² bonded to the same carbon atom taken together may form afunctional group; any two of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹,R¹² R³¹, R³², R³³, R³⁴, R³⁵ and R³⁶ bonded to the same atom or vicinalto one another taken together may form a ring; and when said ligand is(I), Y is C(O), Z is O, and R¹ and R² are each independentlyhydrocarbyl, then R¹ and R² are each independently an aryl substitutedin one position vicinal to the free bond of the aryl group, or R¹ and R²each independently have an E_(s) of −1.0 or less.
 2. The process ofclaim 1, wherein said transition metal is Ni, Pd, Pt, Fe, Co, Ti, Zr, V,Hf, Cr or Cu.
 3. The process of claim 2, wherein said transition metalis Ni, Pd, Ti or Zr.
 4. The process of claim 1, wherein the ligand is(I) and: the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or the transition metal is Ti, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or the transition metal is Zr, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹ R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl,R¹² is hydrocarbyl, substituted hydrocarbyl or a functional group, and Zis O; or the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, R⁷ is hydrocarbyl or substituted hydrocarbyl, Y is CR¹¹R¹²,R¹¹ is hydrogen, R¹² is hydrocarbyl or substituted hydrocarbyl, and Z isN; or the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are oxo, and Z is O;or the transition metal is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen,R⁷ is hydrocarbyl or substituted hydrocarbyl, Y is CR¹¹R¹², R¹¹ and R¹²taken together are oxo, and Z is N; or the transition metal is Ni, m is0, n is 1, R³ and R⁴ are hydrogen, Y is S(T), T is ═O and Z is O; or thetransition metal is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isS(T), T is ═N-silyl, Z is N and R⁷ is silyl; or the transition metal isNi, m is 0, n is 1, R³ and R⁴ are hydrogen, Y is S(T), T is ═O, Z is N,and R⁷ is hydrocarbyl or substituted hydrocarbyl; or the transitionmetal is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹and R¹² taken together are a ring and Z is O; or the transition metal isNi, m is 0, n is 1, R³ and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹ and R¹²taken together are N-hydrocarbyl- or N-substituted hydrocarbylimino, Zis N and R⁷ is hydrocarbyl or substituted hydrocarbyl; or the transitionmetal is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y is S(T), T is ═Oand Z is O; or the transition metal is Ni, m is 0, n is 1, R³ and R⁴ arehydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are sulfo, Z is N andR⁷ is hydrocarbyl or substituted hydrocarbyl.
 5. A process for thepolymerization of olefins, comprising the step of contacting, at atemperature of about −100° C. to about +200° C, at least onepolymerizable olefin with a compound of the formula (IV), (V) or (XIII)

wherein: R¹ and R² are each independently hydrocarbyl, substitutedhydrocarbyl or a functional group; Y is CR¹¹R¹², S(T), S(T)₂, P(T)Q,NR³⁶ or NR³⁶NR³⁶; X is O, CR⁵R⁶ or NR⁵; A is O, S, Se, N, P or As; Z isO, Se, N, P or As; each Q is independently hydrocarbyl or substitutedhydrocarbyl; R³, R⁴, R⁵, R⁶, R¹¹and R¹² are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group; R⁷ ishydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group,provided that when Z is O or Se, R⁷ is not present; R⁸ and R⁹ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group; R¹⁰ is hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group; each T is independently ═O or ═NR³⁰; R³⁰ ishydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;R³¹ and R³² are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; R³³ and R³⁴ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that each isindependently an aryl substituted in at least one position vicinal tothe free bond of the aryl group, or each independently has an E_(s) of−1.0 or less; R³⁵ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that when A is O, S or Se, R³⁵ is notpresent; each R³⁶ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; m is 0 or 1; s is 0 or 1; n is 0 or1; and q is 0 or 1; M is a Group 3 through Group 11 transition metal ora lanthanide metal; and L¹ is a monodentate monoanionic ligand intowhich an ethylene molecule may insert between L¹ and M, and L² is amonodentate neutral ligand which may be displaced by ethylene or anempty coordination site, or L¹ and L² taken together are a monoanionicbidentate ligand into which ethylene may insert between said monoanionicbidentate ligand and said nickel atom, and each L³ is independently amonoanionic ligand and z is the oxidation state of M minus 2; andprovided that; any two of R³, R⁴, R⁵, R⁶, R⁸, R⁹, R¹¹ and R¹² bonded tothe same carbon atom taken together may form a functional group; any twoof R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹, R¹², R³¹, R³², R³³, R³⁴,R^(35 and R) ³⁶ bonded to the same atom or vicinal to one another takentogether may form a ring; and when said compound is (IV), Y is C(O), Zis O, and R¹ and R² are each independently hydrocarbyl, then R¹ and R²are each independently an aryl substituted in one position vicinal tothe free bond of the aryl group, or R¹ and R² each independently have anE_(s) of −1.0 or less.
 6. The process of claim 5, wherein M is Ni, Pd,Pt, Fe, Co, Ti, Zr, V, Hf, Cr or Cu.
 7. The process of claim 6, whereinM is Ni, Pd, Ti or Zr.
 8. The process of claim 5, wherein the compoundis (IV) and: M is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isCR¹¹R¹², R¹¹ is hydrocarbyl or substituted hydrocarbyl, R¹² ishydrocarbyl, substituted hydrocarbyl or a functional group, and Z is O;or M is Ti, m is 0, n is 1, R³ and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹ ishydrocarbyl or substituted hydrocarbyl, R¹² is hydrocarbyl, substitutedhydrocarbyl or a functional group, and Z is 0; or M is Zr, m is 0, n is1, R³ and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹ is hydrocarbyl orsubstituted hydrocarbyl, R¹² is hydrocarbyl, substituted hydrocarbyl ora functional group, and Z is O; or M is Ni, m is 0, n is 1, R³ and R⁴are hydrogen, R⁷ is hydrocarbyl or substituted hydrocarbyl, Y isCR¹¹R¹², R¹¹ is hydrogen, R¹² is hydrocarbyl or substituted hydrocarbyl,and Z is N; or M is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isCR¹¹R¹², R¹¹ and R¹² taken together are oxo, and Z is O; or M is Ni, mis 0, n is 1, R³ and R⁴ are hydrogen, R⁷ is hydrocarbyl or substitutedhydrocarbyl, Y is CR¹¹R¹², R¹¹ and R¹² taken together are oxo, and Z isN; or M is Ni, m is 0, n is 1, R3 and R⁴ are hydrogen, Y is S(T), T is═O and Z is O; or M is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isS(T), T is ═N-silyl, Z is N and R⁷ is silyl; or M is Ni, m is 0, n is 1,R³ and R4 are hydrogen, Y is S(T), T is ═O, Z is N, and R⁷ ishydrocarbyl or substituted hydrocarbyl; or M is Ni, m is 0, n is 1, R³and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together are a ringand Z is O; or M is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isCR¹¹R¹², R¹¹ and R¹² taken together are N-hydrocarbyl- or N-substitutedhydrocarbylimino, Z is N and R⁷ is hydrocarbyl or substitutedhydrocarbyl; or M is Ni, m is 0, n is 1, R³ and R⁴ are hydrogen, Y isS(T), T is ═O and Z is O; or the transition metal is Ni, m is 0, n is 1,R³ and R⁴ are hydrogen, Y is CR¹¹R¹², R¹¹ and R¹² taken together aresulfo, Z is N and R⁷ is hydrocarbyl or substituted hydrocarbyl.
 9. Apolymerization catalyst component comprising a Group 3 through 11transition metal or lanthanide metal complex of a ligand of the formula

wherein: R¹ and R² are each independently hydrocarbyl, substitutedhydrocarbyl or a functional group; Y is CR¹¹R¹², S(T), S(T)₂, P(T)Q,NR³⁶ or NR³⁶NR³⁶; X is O, CR⁵R⁶ or NR⁵; A is O, S, Se, N, P or As; Z isO, Se, N, P or As; each Q is independently hydrocarbyl or substitutedhydrocarbyl; R³, R⁴, R⁵, R⁶, R¹¹and R¹² are each independently hydrogen,hydrocarbyl, substituted hydrocarbyl or a functional group; R⁷ ishydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group,provided that when Z is O or Se, R⁷ is not present; R⁸ and R⁹ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group; R¹⁰ is hydrogen, hydrocarbyl, substituted hydrocarbylor a functional group; each T is independently ═O or ═NR³⁰; R³⁰ ishydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;R³¹ and R³² are each independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; R³³ and R³⁴ are each independentlyhydrocarbyl or substituted hydrocarbyl, provided that each isindependently an aryl substituted in at least one position vicinal tothe free bond of the aryl group, or each independently has an E_(s) of−1.0 or less; R³⁵ is hydrogen, hydrocarbyl, substituted hydrocarbyl or afunctional group, provided that when A is O, S or Se, R³⁵ is notpresent; each R³⁶ is independently hydrogen, hydrocarbyl, substitutedhydrocarbyl or a functional group; m is 0 or 1; s is 0 or 1; n is 0 or1; and q is 0 or 1; and provided that: any two of R³, R⁴, R⁵, R⁶, R⁸ ,R⁹, R¹¹ and R¹² bonded to the same carbon atom taken together may form afunctional group; any two of R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹¹,R¹² R³¹, R³², R³³, R³⁴, R³⁵ and R³⁶ bonded to the same atom or vicinalto one another taken together may form a ring; and when said ligand is(I), Y is C(O), Z is O, and R¹ and R² are each independentlyhydrocarbyl, then R¹ and R² are each independently an aryl substitutedin one position vicinal to the free bond of the aryl group, or R¹ and R²each independently have an E_(s) of −1.0 or less.
 10. The component ofclaim 9, which is on a solid support.
 11. The component of claim 9,wherein a cocatalyst which is an alkylaluminum compound or a borane orboth is also present.
 12. A process for forming an ethylene/polarmonomer copolymer, comprising the step of contacting, under polymerizingconditions, a nickel complex of a bidentate neutral ligand or abidentate monoanionic ligand, with a monomer component comprising one ormore hydrocarbon olefins and one or more polar comonomers (and otheroptional components such as, for example, one or more cocatalysts and/orother additives), at a temperature of about 60° C. to about 170° C.,provided that when CO is present, at least one other polar monomer ispresent.
 13. The process of claim 12, wherein ethylene is present and anethylene partial pressure of at least about 0.67 MPa is used.
 14. Theprocess of claim 12, wherein said one or more polar comonomers comprisesH₂C═CHR²⁰C(O)Y, or H₂C═CR²⁵C(O)Y, wherein R²⁰ is alkylene or substitutedalkylene, R²⁵ is hydrogen, and Y is —OH, —NR²¹R²², —OR²³, or —SR²⁴,wherein R²¹ and R²² are each independently hydrogen, hydrocarbyl orsubstituted hydrocarbyl, R²³ and R²⁴ are each hydrocarbyl or substitutedhydrocarbyl.
 15. The process of claim 12, wherein said bidentate ligandis

wherein: R²⁶ and R²⁷ are each independently hydrocarbyl or substitutedhydrocarbyl, provided that the carbon atom bound to the imino nitrogenatom has at least two carbon atoms bound to it; R²⁸ and R²⁹ are eachindependently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R²⁸ andR²⁹ taken together are hydrocarbylene or substituted hydrocarbylene toform a carbocyclic ring; R⁶⁰ and R⁶¹ are each independently functionalgroups bound to the rest of (XV) through heteroatoms (for example O, Sor N), or R⁶⁰ and R⁶¹ (still containing their heteroatoms) takentogether form a ring. each R⁵⁰ is independently hydrocarbyl orsubstituted hydrocarbyl; each R⁵¹ is independently hydrogen, hydrocarbylor substituted hydrocarbyl; and each R⁵² is hydrocarbyl, substitutedhydrocarbyl, hydrocarbyloxy, or substituted hydrocarbyloxy.
 16. Apolymer, consisting essentially of repeat units derived from ethylene,and one or more polar olefins of the formula H₂C═CHC(O)R³², wherein R³²is —OR³⁴ or any group readily derivable from it, and R³⁴ is hydrocarbylor substituted hydrocarbyl, wherein: said polymer contains “firstbranches” of the formula —(CH₂)_(n)CH₃ and “second branches” of theformula —(CH₂)_(m)C(O)R³², wherein m and n are independently zero or aninteger of 1 or more; and said polymer has the following structuralcharacteristics: (a) one or both of: (1) the ratio of first brancheswherein n is 0 to first branches wherein n is 1 is about 3.0 or more;and (2) the ratio of first branches wherein n is 0 to first brancheswherein n is 3 is 1.0 or more; and (b) one or both of: (1) the totalnumber of first branches in which n is 0, 1, 2 and 3 in said polymer isabout 10 or more per 1000 CH₂ groups; and (2) the incorporation ofrepeat units derived from H₂C═CHC(O)R³² is 0.3 mole percent or morebased on the total repeat units derived from the hydrocarbonolefin andH₂C═CHC(O)R³².
 17. A polymer, consisting essentially of repeat unitsderived from: one or more hydrocarbon olefins, such as ethylene, and oneor more polar olefins of the formula H₂C═CHC(O)R³², wherein R³² is—OR³⁴, or any group readily derivable from it, and R³⁴ is hydrocarbyl orsubstituted hydrocarbyl; wherein in said polymer incorporation of repeatunits derived from H₂C═CHC(O)R³² is 0.3 mole percent or more based onthe total repeat units; and wherein said polymer has one or both of thefollowing structural characteristics: at least 5 mole percent of saidrepeat units derived from H₂C═CHC(O)R³² are present in said polymer asend groups; and said end groups are at least 0.001 mole percent of thetotal repeat units in said polymer; and provided that said end groupshave the formula ˜˜˜˜˜˜˜—HC═CH—C(O)—R³² wherein ˜˜˜˜˜˜˜ is the remainderof the polymer chain of said end group.
 18. A polymer, consistingessentially of: repeat units derived from ethylene; repeat units derivedfrom one or more monomers of the formula H₂C═CHC(O)R³², wherein each R³²is independently —OR³⁴ or any group readily derivable from it, and eachR³⁴ is independently hydrocarbyl or substituted hydrocarbyl, and repeatunits derived from one or more alpha-olefins of formulasH₂C═CH—(CH₂)_(t)—H and/or H₂C═CH—R⁷⁵—G, wherein t is an integer of 1 to20, R⁷⁵ is alkylene or substituted alkylene, and G is an inertfunctional group.